WO2023167134A1

WO2023167134A1 - Electrolysis tank

Info

Publication number: WO2023167134A1
Application number: PCT/JP2023/007044
Authority: WO
Inventors: 秀成石丸; 裕史井上
Original assignee: 株式会社トクヤマ
Priority date: 2022-03-04
Filing date: 2023-02-27
Publication date: 2023-09-07
Also published as: TW202342824A; JP7467519B2; CN118591661A; JP2023128951A

Abstract

Provided is a new and improved electrolysis cell in which, compared to conventional electrolysis tanks, a cathode plate and an anode plate are relatively large with respect to the sizes of a cathode frame and an anode frame, and the electrolysis efficiency is thus improved due to a large relative current-carrying area of the cathode plate and anode plate with respect to the size of the electrolysis tank. An upper opening and a lower opening are respectively formed at the upper end and the lower end of an inner surface, of the cathode frame, to which the cathode plate is fixed, and similarly, an upper opening and a lower opening are respectively formed at the upper end and lower end of the inner surface, of the anode frame, to which the anode plate is fixed. Each of the cathode plate and the anode plate extends continuously from above the upper opening to below the lower opening, and an upper through-opening and a lower through-opening aligned with the upper opening and the lower opening are formed in each of the cathode plate and the anode plate.

Description

electrolytic cell

TECHNICAL FIELD The present invention relates to an electrolytic cell, and more particularly, but not exclusively, to an electrolytic cell that can be suitably used to produce an aqueous quaternary ammonium hydroxide solution using an aqueous quaternary ammonium salt solution as a raw material. .

Patent Documents 1 to 4 below disclose production methods for producing an aqueous quaternary ammonium hydroxide solution using an aqueous quaternary ammonium salt solution as a raw material. An electrolytic cell comprising a cathode frame, a cathode plate fixed to the inner surface of the cathode frame, an anode frame, and an anode plate fixed to the inner surface of the anode frame is used to carry out such a manufacturing method. be done. At least one cation exchange membrane is disposed between the cathode plate and the anode plate. Each chamber partitioned by an ion-exchange membrane is equipped with a flow path for supplying liquid, and a liquid supply and discharge port is provided at any point on the outer surface of the electrolytic cell, and from the opening in contact with each chamber liquid supply and liquid drainage are performed. For example, the cathode frame has a plurality of upper flow passages extending from a plurality of upper openings arranged at intervals in the width direction and a plurality of flow passages extending from a plurality of lower openings arranged at intervals in the width direction. Similarly, the anode frame has a plurality of upper passages extending from a plurality of upper openings spaced apart in the width direction, and a plurality of upper passages spaced apart in the width direction. A plurality of lower flow passages are provided extending from a plurality of lower openings arranged in a row. The cathode plate and the anode plate are rectangular plate-shaped, and are arranged in a region between the upper opening and the lower opening. The upper edges of the cathode plate and the anode plate are positioned below the upper opening, and the lower edges of the cathode plate and the anode plate are positioned above the lower opening. An aqueous quaternary ammonium hydroxide solution is circulated through the lower and upper channels provided in the cathode frame (more specifically, the aqueous quaternary ammonium hydroxide solution is provided in the cathode frame). flow through one of the upper and lower flow channels and out through the other). In addition, for example, an aqueous quaternary ammonium salt solution, which is a raw material, is circulated through the upper channel and the lower channel provided in the anode frame (more specifically, for example, the aqueous quaternary ammonium salt solution, which is a raw material, is circulated). It flows in through one of the upper channel and the lower channel disposed in the anode frame and outflows through the other).

JP-A-62-142792 Japanese Patent Publication No. 8-16274 Japanese Patent Publication No. 8-19539 JP 2009-13477 A

Thus, in the conventional electrolytic cell as described above, the cathode plate and the anode plate are provided between the upper and lower openings of the cathode frame and between the upper and lower openings of the anode frame, respectively. Since it is arranged between the cathode plate and the anode plate, the size of the cathode plate and the anode plate is limited with respect to the size of the cathode frame and the anode frame, and the relative current-carrying area of the cathode plate and the anode plate with respect to the size of the electrolytic cell. is limited and the electrolysis efficiency is not always sufficient.

The present invention has been made in view of the above-mentioned facts, and its main technical problem is that the size of the cathode plate and the anode plate is relative to the size of the cathode frame and the anode frame compared to the conventional electrolytic cell. To provide a new and improved electrolytic cell which is large in area and therefore has a large relative current-carrying area of the cathode plate and the anode plate with respect to the size of the electrolytic cell and improved electrolysis efficiency.

Another technical object of the present invention is, in addition to achieving the main technical objects described above, to provide a gasket interposed between the cathode frame and the cathode plate and the anode frame and the anode even if the electrolytic cell is continuously operated. To provide a novel and improved electrolytic cell in which fluid flow is not hindered by a gasket interposed between plates.

Still another technical object of the present invention, in addition to the above main technical object and the above other technical objects, is to provide a new and improved electrochemical corrosion and corrosion of the cathode plate and the anode plate effectively avoided. It is to provide an electrolytic cell.

As a result of intensive studies, the inventors of the present invention formed upper and lower openings in the upper and lower ends of the inner surface of the cathode frame to which the cathode plate is fixed, and similarly fixed the anode plate in the anode frame. An upper opening and a lower opening are formed at the upper end and the lower end of the inner surface, respectively, and each of the cathode plate and the anode plate continuously extends from above the upper opening to below the lower opening. It has been found that the main technical object can be achieved by forming an upper through-opening and a lower through-opening matching the upper opening and the lower opening in each of the cathode plate and the anode plate.

That is, according to the present invention, as an electrolytic cell that achieves the above main technical problems,
An electrolytic cell comprising a cathode frame, a cathode plate fixed to the inner surface of the cathode frame, an anode frame, and an anode plate fixed to the inner surface of the anode frame,
The cathode frame has at least one upper channel extending from an upper opening located at the upper end of the inner surface and at least one lower channel extending from a lower opening located at the lower end of the inner surface. is set,
At least one upper channel extending from an upper opening located at the upper end of the inner surface and at least one lower channel extending from a lower opening located at the lower end of the inner surface are arranged in the anode frame. is set,
the cathode plate extends continuously from above the upper opening of the cathode frame to below the lower opening of the cathode frame;
The upper end of the cathode plate is formed with at least one upper through opening aligned with the upper opening of the cathode frame, and the lower end of the cathode plate is formed with the lower opening of the cathode frame. at least one matching lower through opening is formed;
The anode plate extends continuously from above the upper opening of the anode frame to below the lower opening of the anode frame,
The upper end of the anode plate is formed with at least one upper through-opening aligned with the upper opening of the anode frame, and the lower end of the anode plate is formed with the lower opening of the anode frame. at least one matching lower through opening is formed;
There is provided an electrolytic cell characterized by:

Preferably, the cathode frame has a plurality of upper flow passages extending from a plurality of upper openings spaced apart in the width direction at the upper end of the inner surface, and a plurality of upper flow channels spaced apart in the lower end of the inner surface in the width direction. a plurality of lower flow passages extending from the plurality of lower openings arranged at intervals of
The anode frame has a plurality of upper flow passages extending from a plurality of upper openings arranged at intervals in the width direction at the upper end of the inner surface and at the lower end of the inner surface at intervals in the width direction. a plurality of lower flow passages extending from the plurality of arranged lower openings,
The upper end of the cathode plate is formed with a plurality of upper through-openings aligned with the plurality of upper openings of the cathode frame, and the lower end of the cathode plate is formed with a plurality of upper through-openings. a plurality of lower through-openings are formed in alignment with each of the plurality of lower openings;
The upper end of the anode plate is formed with a plurality of upper through-openings that are respectively aligned with the plurality of upper openings of the anode frame, and the lower end of the anode plate is formed with the anode frame. A plurality of lower through openings are formed in alignment with each of the plurality of lower openings.
the upper opening and the lower opening of the cathode frame and the upper through-opening and the lower through-opening of the cathode plate have a circular cross-sectional shape;
Advantageously, the upper and lower openings of the anode frame and the upper and lower through-openings of the anode plate have a circular cross-sectional shape.
Advantageously, the cathode plate and the anode plate consist of rectangular plates.

The other technical problem of the present invention is to solve the above-described electrolytic cell,
A gasket is interposed between the cathode frame and the cathode plate, and the gasket includes an upper communication opening communicating between the upper opening of the cathode frame and the upper through opening of the cathode plate, and the cathode frame. a lower communicating opening communicating between the lower opening of the body and the lower through opening of the cathode plate;
A gasket is interposed between the anode frame and the anode plate, and the gasket includes an upper communication opening communicating between the upper opening of the anode frame and the upper through opening of the anode plate, and the anode frame. a lower communication opening communicating with the lower opening of the body and the lower through-opening of the anode plate,
the upper communication opening is larger than the upper opening and the upper through-opening, and the lower communication opening is larger than the lower opening and the lower through-opening;
Accomplished by form.

The upper opening, the upper through-opening, the upper communication opening, and the lower opening, the lower through-opening, and the lower communication opening preferably have a circular cross-sectional shape.

Still another technical problem of the present invention is that in the electrolytic cell,
In each of the upper through-opening and the lower through-opening of the cathode plate and the upper through-opening and the lower through-opening of the anode plate, an inner peripheral surface of each of the upper through-opening and the lower through-opening is provided. A covering member is attached to cover the portion adjacent to each of the upper through-opening and the lower through-opening on the back surface of the cathode plate and the anode plate and not covered by the gasket,
Accomplished by form.

Preferably, each of the covering members has a tubular portion inserted into each of the upper through-hole or the lower through-opening and a flange projecting from the rear end of the tubular portion.
The cylindrical portion of the covering member has a cylindrical shape, and the upper opening, the upper through-opening, the upper communication opening, the lower opening, the lower through-opening, and the lower communication opening have a circular cross-sectional shape,
The inner diameters of the upper through-opening and the lower through-opening are larger than the inner diameters of the upper opening and the lower opening, respectively, by twice the thickness of the cylindrical portion of the covering member. the inner diameter is the same as the inner diameters of the upper opening and the lower opening;
The length of the cylindrical portion is the same as the thickness of the cathode plate,
The flange portion of the covering member has an annular shape, and the outer diameter of the flange portion is the same as the inner diameters of the upper communication opening and the lower communication opening,
The thickness of the flange portion is preferably the same as the thickness of the gasket.
Advantageously, each of the covering members is made of synthetic resin.

In a preferred mode of use of the above electrolytic cell, at least one cation exchange membrane is arranged between the cathode plate and the anode plate, and an aqueous quaternary ammonium hydroxide solution is prepared using an aqueous quaternary ammonium salt solution as a raw material. is manufactured.

In the electrolytic cell constructed according to the present invention, which achieves the above main technical object, each of the cathode plate and the anode plate is arranged from above the upper opening formed in the cathode frame and the anode frame from the lower opening. The cathode plate and the anode plate are formed with an upper through-opening and a lower through-opening matching the upper opening and the lower opening, respectively. It extends over substantially the entire inner surface of the cathode frame and the anode frame, so that the current-carrying area of the cathode plate and the anode plate is large relative to the size of the electrolytic cell, and the electrolysis efficiency is improved.

In the electrolytic cell constructed according to the present invention, which achieves the above technical object, the upper communicating opening is larger than the upper opening and the upper through opening, and the lower communicating opening is larger than the lower opening and the lower through opening. Therefore, even if the gasket expands due to continuous operation of the electrolytic cell, the communication between the upper opening and the upper through opening and the communication between the lower opening and the lower through opening are not hindered.

In the electrolytic cell constructed according to the present invention, which achieves the above-mentioned further technical object, each of the upper through-opening and lower through-opening of the cathode plate and the upper through-opening and lower through-opening of the anode plate includes: A coating that covers the inner peripheral surface of each of the upper through-opening and the lower through-opening, and also covers the portions that are adjacent to the upper through-opening and the lower through-opening on the back surfaces of the cathode plate and the anode plate and that are not covered by the gasket. Electrolytic corrosion and corrosion of the cathode and anode plates are effectively avoided due to the attachment of the members.

1 is a simplified cross-sectional view of a preferred embodiment of an electrolytic cell constructed in accordance with the present invention; FIG. 2 is a simplified cross-sectional view along line II-II in FIG. 1 showing the cathode frame and cathode plate in the electrolytic cell shown in FIG. 1; FIG. FIG. 2 is a partially enlarged cross-sectional view showing the cathode frame upper opening, the upper through opening formed in the cathode plate, and the upper communicating opening formed in the gasket in the electrolytic cell shown in FIG. 1 ; FIG. 4 is a partially enlarged cross-sectional view showing a modified example in which a covering member is attached to the upper through-hole of the cathode plate (and anode plate). FIG. 5 is a perspective view showing the covering member shown in FIG. 4;

A more detailed description will now be given with reference to the accompanying drawings, which illustrate preferred embodiments of electrolytic cells constructed in accordance with the present invention.

1 and 2, the illustrated electrolytic cell constructed in accordance with the present invention includes a cathode frame 4 (FIG. 1), an anode frame 6 (FIG. 1), a cathode side upper wall member 8, an anode Side upper wall member 10, cathode side lower wall member 12, anode side lower wall member 14, cathode side front wall member 16 (FIG. 2), anode side front wall member (not shown), cathode side rear wall member 18 ( 2) and an anode-side rear wall member (not shown). The cathode frame 4, the anode frame 6, the cathode-side front wall member 16, the anode-side front wall member, the cathode-side rear wall member 18, and the anode-side rear wall member extend substantially vertically. , the anode-side upper wall member 10, the cathode-side lower wall member 12 and the anode-side lower wall member 14 extend substantially horizontally. The base end surface (the right end surface in FIG. 1) of the cathode-side upper wall member 8 is connected to the upper edge of the inner surface of the cathode frame 4 by a suitable connection means such as a fastening screw or adhesive. The base end surface (the right end surface in FIG. 1) is connected to the lower edge of the inner surface of the cathode frame 4 by suitable connecting means. Similarly, the base end surface of the anode-side upper wall member 10 (the left end surface in FIG. 1) is connected to the upper edge of the inner surface of the anode frame 6 by a suitable connecting means, and the base end surface of the anode-side lower wall member 14 (the left end surface in FIG. 1) 1) is connected to the lower edge of the inner surface of the anode frame 6 by an appropriate connecting means. The cathode-side front wall member 16 is connected to the front surface of the cathode frame 4, the anode-side front wall member is connected to the front surface of the anode frame 6, and the cathode-side rear wall member 18 is connected to the rear surface of the cathode frame 4. Furthermore, the anode-side rear wall member is connected to the rear surface of the anode frame 6 by appropriate connecting means. The cathode-side and anode-side

upper wall members

8 and 10,

lower wall members

12 and 14, front wall member 16 and rear wall member 18, respectively, are connected to the cathode frame 4 or the anode frame 6 as described above. Alternatively, these wall members may be integrally formed in advance and connected to the cathode frame 4 or the anode frame 6 . Moreover, the wall portion can be formed integrally with the cathode frame 4 or the anode frame 6 . Furthermore, when the

upper wall members

8 and 10, the

lower wall members

12 and 14, the front wall member 16 and the rear wall member 18 are integrally formed, a sealing member is interposed between the cathode frame 4 or the anode frame 6. It can also be fixed. As a sealing member, an extension part can be used by extending a gasket 38 described later from a size corresponding to the cathode plate 32 or the anode plate 56 to a size corresponding to the cathode frame 4 or the anode frame 6 . Cathode frame 4, anode frame 6, cathode-side upper wall member 8, anode-side upper wall member 10, cathode-side lower wall member 12, anode-side lower wall member 14, cathode-side front wall member 16, anode-side front wall member The cathode-side rear wall member 18 and the anode-side rear wall member 18 may be in the form of solid blocks or plates, except for openings and channels to be described later, and may be made of olefin resins such as polypropylene and polyethylene, vinyl chloride resins, and fluorine resins. It can be formed from an appropriate synthetic resin such as. Cathode frame 4, anode frame 6, cathode-side upper wall member 8, anode-side upper wall member 10, cathode-side lower wall member 12, anode-side lower wall member 14, cathode-side front wall member 16, anode-side front wall member A suitable sealing member (not shown) such as a gasket may be interposed between the interconnecting portions of the cathode side rear wall member 18 and the anode side rear wall member.

3 together with FIGS. 1 and 2, the inner surface of the cathode frame 4 (the right side in FIG. 1) is provided at the upper end in the width direction (the direction perpendicular to the paper surface in FIG. A plurality of (three in the illustrated case) upper openings 20 (one of which is shown by a broken line and a solid line in FIGS. 1 and 3, respectively) are formed at equal intervals in the horizontal direction in the The cathode frame 4 has a plurality of (three in the illustrated case) upper flow passages 22 extending from each of the upper openings 20 substantially horizontally through the cathode frame 4. (one of which is shown in dashed and solid lines, respectively) are formed. Similarly, on the lower end of the inner surface (right side in FIG. 1) of the cathode frame 4, a plurality of electrodes (in the figure) are spaced equally in the width direction (the direction perpendicular to the paper surface in FIG. 1, the left and right direction in FIG. 2). (three in the case of 1) are formed with lower openings 24 (one of which is shown in dashed lines in FIG. 1), and the cathode frame 4 extends substantially horizontally from each of the lower openings 24. A plurality of (three in the illustrated case) lower flow paths 26 (one of which is shown by broken lines in FIG. 1) extending through the frame 4 are formed. Upper opening 20 and lower opening 24 may be circular, and the cross-sectional shape of upper channel 22 and the cross-sectional shape of lower channel 26 may be circular to match the circular shape of upper opening 20 and lower opening 24 . The upper flow path 22 and the lower flow path 26 are connected by an outer flow path 31 (a part of which is shown in FIG. 2) disposed outside the housing 2. The outer flow path 31 Also provided are a circulation pump, a product storage tank, and a plurality of valve members for flow control (the outer flow path and the above-described components disposed thereon will be familiar to those skilled in the art). Since they are well known, a detailed description thereof is omitted here).

A cathode plate 32 is fixed to the inner surface of the cathode frame 4 . It is important that the cathode plate 32 continuously extends from above the upper opening 20 formed in the cathode frame 4 to below the lower opening 24 formed in the cathode frame 4. is. In the illustrated embodiment, the cathode plate 32 is composed of a rectangular plate made of a suitable conductive metal such as nickel, the upper end surface of which is in contact with the inner surface (that is, the lower surface) of the cathode-side upper wall member 8. the lower end surface abuts or approaches the inner surface (i.e., upper surface) of the cathode-side lower wall member 12, and the front side surface abuts or approaches the inner surface (i.e., rear surface) of the front wall member 16; The rear side surface abuts or is close to the inner surface (that is, the front surface) of the rear wall member 18 . The cathode plate 32 can be conveniently fixed to the cathode frame 4 by, for example, screwing fastening screws (not shown) into the cathode frame 4 through the cathode plate 32 at the four corners of the cathode plate 32 . can. At the upper end of the cathode plate 32, a plurality of (three in the illustrated case) upper through-holes 34 are formed at equal intervals in the width direction (the direction perpendicular to the paper surface in FIG. 1 and the left-right direction in FIG. 2). At the lower end of the cathode plate 32, a plurality of (three in the illustrated case) lower through openings 36 are provided at equal intervals in the width direction (the direction perpendicular to the paper surface in FIG. 1 and the left-right direction in FIG. 2). formed. It is important that the upper through openings 34 formed in the cathode plate 32 are aligned with the upper openings 20 formed in the upper end of the cathode frame 4, respectively. In the illustrated embodiment, each of the upper through openings 34 is the same shape (and thus circular) and the same size as each of the upper openings 20 described above. Similarly, it is important that each of the lower through openings 36 formed in the cathode plate 32 is aligned with each of the lower openings 24 formed in the lower end of the cathode frame 4. is. In the illustrated embodiment, each of the lower through openings 36 is the same shape (and thus circular) and the same size as each of the lower openings 24 described above. Upper through-opening 34 (and upper opening 20) is preferably located adjacent the upper edge of cathode plate 32 and lower through-opening 36 (and lower opening 24) is preferably located adjacent the lower edge of cathode plate 32. .

In the illustrated embodiment, a plurality of upper openings 20 and lower openings 24 are formed in the cathode frame 4 at equal intervals in the width direction, and a plurality of openings are formed in the cathode plate 32 at equal intervals in the width direction. An upper through-opening 34 and a lower through-opening 36 are formed. It is also possible to form one upper through-opening and one lower through-opening elongated in the direction.

3 together with FIG. 1, in the illustrated embodiment, a gasket 38 is preferably interposed between the cathode frame 4 and the cathode plate 32. The gasket 38 The cathode plate 32 can be stably fixed to the cathode frame 4, and corrosion due to permeation of liquid to the interface between the cathode frame 4 and the cathode plate 32 can be prevented. The gasket 38 may be a rectangular plate having substantially the same dimensions as the cathode plate 32 (as described above, the gasket 38 may also have a size corresponding to that of the cathode frame 4), and is made of an appropriate elastomer such as silicone rubber or ethylene propylene. It can be formed from rubber, chloroprene rubber, soft vinyl chloride, butyl rubber, butadiene rubber or fluororubber. When a gasket 38 is interposed between the cathode frame 4 and the cathode plate 32 , a fastening screw (not shown) is attached to the cathode frame 4 through the gasket 38 together with the cathode plate 32 at the four corners of the cathode plate 32 . Can be screwed on. At the upper end of the gasket 38, a plurality of gaskets (three in the case of the drawing) are provided to communicate with each of the upper through openings 34 formed in the cathode plate 32 and each of the upper openings 20 formed in the cathode frame 4. The lower end of the gasket 38 is formed with each of the lower through openings 36 formed in the cathode plate 32 and each of the lower openings 24 formed in the cathode frame 4. A plurality (three in the illustrated case) of communicating lower communication openings 42 are formed in. As will be clearly understood by referring to FIG. The side communication opening 42 is preferably larger than the upper through opening 34 and the upper opening 20 and the lower through opening 36 and the lower opening 24. As will be understood from the examples described later, the upper communication opening formed in the gasket 38 is If opening 40 and lower communication opening 42 are substantially the same size as upper through-opening 34 and upper opening 20 and lower through-opening 36 and lower opening 24, continuous operation of the electrolytic cell will result in gasket 38 is expanded somewhat to contract and displace the upper communication opening 40 and the lower communication opening 42, thereby causing communication between the upper through-opening 34 and the upper opening 20 and the lower through-opening 36 and the lower opening 24. The upper and

lower communication openings

40, 42 are defined by the diameters of the upper through-

openings

34, 20 and the lower through-

openings

36, 24. Each of the upper communicating opening 40 and the lower communicating opening 42 does not necessarily correspond to each of the upper through opening 34 and the upper opening 20 and the lower through opening 36 and the lower opening 24 respectively. The diameters of the upper and lower communicating

openings

40 and 42 and the degree of eccentricity with respect to the upper through-

openings

34 and 20 and the lower through-

openings

36 and 24 are determined by electrolytic It can be empirically set based on the expansion and displacement of the gasket 38 due to continuous operation of the tank. However, as will be described later, the increase in the area of contact with the liquid on the back surface of the cathode plate 32 causes electrical corrosion or corrosion, and the amount of electrode metal mixed in the liquid increases. Therefore, the preferable size of the upper communication opening 40 and the lower communication opening 42 formed in the gasket 38 is the size of the upper through-opening 34 and the upper opening 20 and the size of the lower through-opening 36 and the lower opening 24 +30 mm. Below, it is preferably +20 mm or less, more preferably +10 mm or less. Also, if the gasket 38 is made of a material that does not easily expand, the sizes of the upper communication opening 40 and the lower communication opening 42 are close to the sizes of the upper through opening 34 and the upper opening 20 and the lower through opening 36 and the lower opening 24. However, the possibility of insufficient or damaged communication is reduced. Therefore, the material used for the gasket 38 preferably has a linear expansion coefficient of 3×10 ⁻⁴ (1/° C.) or less, more preferably 1.5×10 ⁻⁴ (1/° C.) or less, most preferably 1 ×10 ⁻⁴ (1/° C.) or less.

In the illustrated embodiment, the anode frame 6 is substantially the same as the cathode frame 4 described above. More specifically, the cathode frame 4 and the anode frame 6 are plane-symmetrical with respect to a virtual plane extending perpendicularly to the plane of FIG. 1 . Accordingly, the anode frame 6 is provided with an upper opening 44 , an upper flow path 46 , a lower opening 48 and a lower flow path 50 . To avoid duplication of description, a detailed description of upper opening 44, upper channel 46, lower opening 48 and lower channel 50 is omitted. The upper flow path 46 and the lower flow path 50 are connected by an outer flow path (not shown) provided outside the housing 2, and the outer flow path includes a circulation pump and a raw material storage tank. and a plurality of valve members for flow control, etc. (the outer flow path and the above-described components disposed therein are well known to those skilled in the art, so detailed description thereof will be provided.) description is omitted here).

An anode plate 56 is fixed to the inner surface of the anode frame 6 . In the illustrated embodiment, the anode plate 56 is substantially identical to the cathode plate 32 described above, except that it is formed from any suitable conductive metal suitable for an anode, such as titanium plated with indium oxide on its surface. be. More specifically, the cathode plate 32 and the anode plate 56 are plane-symmetrical with respect to a virtual plane extending perpendicularly to the plane of FIG. Therefore, the anode plate 56 has a rectangular shape that continuously extends from above the upper opening 44 formed in the anode frame 6 to below the lower opening 48 formed in the anode frame 6 . be. The anode plate 56 is formed with an upper through-opening 58 and a lower through-opening 60 that are aligned with the upper opening 44 and the lower opening 48 formed in the anode frame 6, respectively. A detailed description of the anode plate 56 is omitted to avoid duplication of description.

In the illustrated embodiment, a gasket 62 is also interposed between the anode frame 6 and the anode plate 56 . This gasket 62 is also substantially the same as the gasket 38 interposed between the cathode frame 4 and the cathode plate 32 . More specifically, the gasket 38 and the gasket 62 are symmetrical with respect to an imaginary plane extending perpendicularly to the plane of the paper in FIG. Therefore, the gasket 62 has an upper opening 44 formed in the anode frame 6 and an upper through-opening 58 formed in the anode plate 56 . A lower communication opening 66 that communicates between the side opening 48 and the lower through opening 60 formed in the anode plate 56 is formed. In order to avoid duplication of description, descriptions of the gasket 62 and the details of the upper communication opening 64 and the lower communication opening 66 are omitted.

As clearly understood by referring to FIG. 1, a cation exchange membrane 68 is arranged between the cathode plate 32 and the anode plate 56 in the illustrated embodiment. The cation exchange membrane 68, which itself may be of a known form, has a rectangular plate shape, the upper edge of which is gripped between the cathode-side upper wall member 8 and the anode-side upper wall member 10, and the lower edge of which is the cathode-side membrane. It is held between the lower wall member 12 and the anode side lower wall member 14, and the front side edges of the cathode frame 4 and the anode frame 6 are held between the cathode side front wall member 16 and the anode side front wall member. , the rear side edges of the cathode frame 4 and the anode frame 6 are held between the cathode side rear wall member 18 and the anode side rear wall member. The cation exchange membrane 68, the cathode-side upper wall member 8 and the anode-side upper wall member 10, the cathode-side lower wall member 12 and the anode-side lower wall member 14, the cathode-side front wall member 16 and the anode-side front wall member, and the cathode-side rear wall member An appropriate sealing member (not shown) can be interposed between the wall member 18 and each of the anode-side rear wall members.

In the electrolytic cell as described above, a cathode or product chamber 70 is defined between the cathode plate 32 and the cation exchange membrane 68, and an anode or feed chamber 72 is defined between the anode plate 56 and the cation exchange membrane 68. stipulated. Then, an initially diluted quaternary ammonium hydroxide aqueous solution (or pure water) is circulated through the product chamber 70. More specifically, the lower channel 26 and the upper channel 22 formed in the cathode frame 4 flows into the product chamber 70 through one of and flows out of the product chamber 70 through the other. At the same time, the aqueous quaternary ammonium salt solution is circulated through the raw material chamber 72, and more specifically, flows into the raw material chamber 72 through one of the lower channel 50 and the upper channel 46 formed in the anode frame 6, and flows through the other. be leaked. An electrolytic voltage is applied between the cathode plate 32 and the anode plate 56 . Thus, the concentration of aqueous quaternary ammonium hydroxide solution circulating in product chamber 70 is gradually increased. Since such electrolytic action is well known to those skilled in the art, a detailed description thereof is omitted herein. Thus, in the electrolytic cell constructed in accordance with the present invention, the cathode plate 32 and the anode plate 56 are positioned from above to below the

upper openings

20 and 44 formed in the cathode frame 4 and the anode frame 6, respectively. Upper through-

openings

34 and 58 aligned with

upper openings

20 and 44 and

lower openings

24 and 48 and lower through-

openings

34 and 58 in cathode plate 32 and anode plate 56, respectively, which extend continuously below

openings

24 and 48, respectively. Due to the through

openings

36 and 60 formed, the cathode plate 32 and the anode plate 56 extend over substantially the entire inner surface of the cathode frame 4 and the anode frame 6, respectively, thus providing a cathode relative to the size of the electrolytic cell. Electrolysis is performed with a large relative current carrying area of plate 32 and anode plate 56, thus improving electrolysis efficiency.

FIG. 4 illustrates a variation of the above-described preferred embodiment of an electrolytic cell constructed in accordance with the present invention. In the modification shown in FIG. 4, the upper through-opening 34 (and the lower through-opening 36) of the cathode plate 32 along with the inner peripheral surface of the upper through-opening 34 (and the lower through-opening 36) in the back surface of the cathode plate 32 (the right surface in FIG. 4). A covering member 74 is attached to the cathode plate 32 adjacent to each of the side through openings 36) and covering the portion not covered by the gasket 38. As shown in FIG. FIG. 4 shows one upper through-opening 34 of the cathode plate 32 and one covering member 74 attached to this upper through-opening 34 . As will be clearly understood by referring to FIG. 5 together with FIG. 4, the illustrated covering member 74 includes a cylindrical tubular portion 76 inserted into the upper through-opening 34 and a rear end of the tubular portion 76 (in FIG. 4). right end) and an annular flange portion 78 projecting from the right end). Each of the covering members 74 is made of a synthetic resin excellent in electrical insulation, heat resistance, and resistance to a circulating quaternary ammonium hydroxide aqueous solution and having a small coefficient of thermal expansion, for example, an olefin resin such as polypropylene or polyethylene, or It is preferably made of a synthetic resin which is a fluororesin such as perfluoroalkoxyalkane (PFA) or polytetrafluoroethylene (PTFE).

In the modification shown in FIG. 4, the inner diameter of the upper through-hole 34 formed in the cathode plate 32 is twice the thickness of the cylindrical portion 76 of the covering member 74, which is the thickness of the upper side formed in the cathode frame 4. It is set larger than the inner diameter of the opening 20 . The outer diameter of the cylindrical portion 76 of the covering member 74 is the same as the inner diameter of the upper through-opening 34 , and the inner diameter of the cylindrical portion 76 of the covering member 74 is the same as the inner diameter of the upper flow path 22 . The length of the tubular portion 76 of the covering member 74 is the same as the thickness of the cathode plate 32 . The outer diameter of the flange portion 78 of the covering member 74 is the same as the inner diameter of the upper communication opening 40 formed in the gasket 38 , and the thickness of the flange portion 78 of the covering member 74 is the same as the thickness of the gasket 38 . If the gasket 38 has high elasticity and is crushed and becomes thin when fixing the cathode plate 32 to the cathode frame 4, the thickness of the flange portion 78 of the covering member 74 is reduced by the thickness of the gasket 38. It is convenient to match the thickness when it becomes. Prior to fixing the cathode plate 32 and the gasket 38 to the cathode frame 4, as shown in FIG. 34 and the front surface (the left surface in FIG. 4) of the flange portion 78 abuts against the back surface of the cathode plate 32 , so that the tubular portion 76 of the covering member 74 is positioned inside the upper through-hole 34 formed in the cathode plate 32 . The peripheral surface is covered, and the flange portion 78 of the covering member 74 covers the portion of the back surface of the cathode plate 32 that is not covered by the gasket 38 .

According to the experience of the present inventors, when the upper through-hole 34 and the lower through-opening 36 of the cathode plate 32 are not provided with the covering member 74, continuous operation of the electrolytic cell results in two cases shown in FIG. As indicated by the dashed line 80, the inner peripheral surfaces of the upper through-hole 34 and the lower through-opening 36 of the cathode plate 32 and the portion of the back surface of the cathode plate 32 not covered with the gasket 38 tend to be electrically corroded or corroded. be. However, if the covering member 74 is attached to each of the upper through-hole 34 and the lower through-opening 36 of the cathode plate 32, the electrolytic corrosion or corrosion of the cathode plate 32 can be effectively avoided.

Although the covering member 74 has been described with respect to the upper through opening 34 of the cathode plate 32, the covering member 74 is also attached to each of the lower through opening 36 of the cathode plate 32 and the upper through opening 58 and the lower through opening 60 of the anode plate 56. can do.

Examples 1 to 6
1 to 3, and an electrolytic cell having the form shown in FIGS. 1 to 3 with a covering member shown in FIGS. Then, the state of the upper and lower communication openings formed in the gasket interposed between the cathode plate and the cathode frame and the concentration of mixed metal (nickel) in the product were detected. Table 1 shows the results.

In the communication opening state in Table 1, "no protrusion" means that the communication opening clogging rate was less than 10%, and "protrusion" means that the communication opening clogging rate was 10% or more and less than complete clogging. and "blocked" means that the communication opening is blocked and the product does not flow.
The details and operating conditions of the electrolytic cell components are as follows.
Operating time: 30 days Cathode: Nickel plate (thickness 2 mm, surface area 1 m x 1 m)
Anode: Titanium plate plated with indium oxide (thickness 2mm, surface area 1m x 1m)
Number of through openings in cathode plate: 10 upper through openings (exit), 10 lower through openings (inlet) Number of through openings in anode plate: 10 upper through openings (exit), lower through openings (inlet) 10 cation exchange membranes: Chemours Company
) under the product name “N324” Replacement membrane (thickness 1 mm)
Raw material: Tetramethylammonium chloride aqueous solution Product: Tetramethylammonium hydroxide aqueous solution Channel cross-sectional shape: Upper and lower openings of the cathode frame and anode frame, upper and lower channels, cathode plate and anode plate The cross-sections of the upper and lower through-holes are all circular with a diameter of 10 mm Covering member: Made of polypropylene, cylinder outer diameter 10 mm, cylinder inner diameter 8 mm, cylinder length 2 mm, flange outer diameter 16
mm, flange thickness 1 mm
Current: 1000A (10A/ ^dm2 )
Operating temperature: 70°C
Temperature when assembling electrolytic cell: 20°C

Although the invention has been described in detail with reference to the accompanying drawings which illustrate preferred embodiments of the invention, the invention is not so limited and various modifications can be made without departing from the scope of the invention. It goes without saying that variations and modifications are possible. For example, in the illustrated embodiment, one cation exchange membrane 68 is disposed between cathode plate 32 and anode plate 56, but multiple exchange membranes 68 are disposed between cathode plate 32 and anode plate 56. The present invention can also be applied to electrolytic cells in which membranes (cation exchange membranes and anion exchange membranes) are arranged.

2: Housing of electrolytic cell 4: Cathode frame 6: Anode frame 8: Cathode side upper wall member 10: Anode side upper wall member 12: Cathode side lower wall member 14: Anode side lower wall member 16: Cathode side front wall Member 18: Cathode Side Rear Wall Member 20: Upper Opening 22: Upper Channel 24: Lower Opening 26: Lower Channel 31: Outer Channel 32: Cathode Plate 34: Upper Penetrating Opening 36: Lower Penetrating Opening 38: : gasket 40: upper communicating opening 42: lower communicating opening 44: upper opening 46: upper channel 48: lower opening 50: lower channel 56: anode plate 58: upper through-opening 60: lower through-opening 62: Gasket 64: upper communication opening 66: lower communication opening 68: cation exchange membrane 70: product chamber (cathode chamber)
72: raw material chamber (anode chamber)
74: Coating member 76: Cylindrical portion 78: Flange portion 80: Electrolytic corrosion or corrosion state

Claims

An electrolytic cell comprising a cathode frame, a cathode plate fixed to the inner surface of the cathode frame, an anode frame, and an anode plate fixed to the inner surface of the anode frame,
The cathode frame has at least one upper channel extending from an upper opening located at the upper end of the inner surface and at least one lower channel extending from a lower opening located at the lower end of the inner surface. is set,
At least one upper channel extending from an upper opening located at the upper end of the inner surface and at least one lower channel extending from a lower opening located at the lower end of the inner surface are arranged in the anode frame. is set,
the cathode plate extends continuously from above the upper opening of the cathode frame to below the lower opening of the cathode frame;
The upper end of the cathode plate is formed with at least one upper through opening aligned with the upper opening of the cathode frame, and the lower end of the cathode plate is formed with the lower opening of the cathode frame. at least one matching lower through opening is formed;
The anode plate extends continuously from above the upper opening of the anode frame to below the lower opening of the anode frame,
The upper end of the anode plate is formed with at least one upper through-opening aligned with the upper opening of the anode frame, and the lower end of the anode plate is formed with the lower opening of the anode frame. at least one matching lower through opening is formed;
An electrolytic cell characterized by:
The cathode frame has a plurality of upper flow passages extending from a plurality of upper openings spaced apart in the width direction at the upper end of the inner surface and at the lower end of the inner surface at intervals in the width direction. a plurality of lower flow passages extending from the plurality of arranged lower openings,
The anode frame has a plurality of upper flow passages extending from a plurality of upper openings arranged at intervals in the width direction at the upper end of the inner surface and at the lower end of the inner surface at intervals in the width direction. a plurality of lower flow passages extending from the plurality of arranged lower openings,
The upper end of the cathode plate is formed with a plurality of upper through-openings aligned with the plurality of upper openings of the cathode frame, and the lower end of the cathode plate is formed with a plurality of upper through-openings. a plurality of lower through-openings are formed in alignment with each of the plurality of lower openings;
The upper end of the anode plate is formed with a plurality of upper through-openings that are respectively aligned with the plurality of upper openings of the anode frame, and the lower end of the anode plate is formed with the anode frame. a plurality of lower through-openings respectively aligned with each of the plurality of lower openings;
The electrolytic cell according to claim 1.
the upper opening and the lower opening of the cathode frame and the upper through-opening and the lower through-opening of the cathode plate have a circular cross-sectional shape;
the upper opening and the lower opening of the anode frame and the upper through-opening and the lower through-opening of the anode plate have a circular cross-sectional shape;
The electrolytic cell according to claim 1 or 2.
The electrolytic cell according to any one of claims 1 to 3, wherein the cathode plate and the anode plate are rectangular plates.
A gasket is interposed between the cathode frame and the cathode plate, and the gasket includes an upper communication opening communicating between the upper opening of the cathode frame and the upper through opening of the cathode plate, and the cathode frame. a lower communicating opening communicating between the lower opening of the body and the lower through opening of the cathode plate;
A gasket is interposed between the anode frame and the anode plate, and the gasket includes an upper communication opening communicating between the upper opening of the anode frame and the upper through opening of the anode plate, and the anode frame. A lower communication opening is formed that communicates with the lower opening of the body and the lower through-opening of the anode plate,
An electrolytic cell according to any one of claims 1 to 4.
the upper communication opening is larger than the upper opening and the upper through-opening, and the lower communication opening is larger than the lower opening and the lower through-opening;
The electrolytic cell according to claim 5.
The upper opening, the upper through-opening, the upper communication opening, and the lower opening, the lower through-opening, and the lower communication opening have a circular cross-sectional shape,
The electrolytic cell according to claim 6.
In each of the upper through-opening and the lower through-opening of the cathode plate and the upper through-opening and the lower through-opening of the anode plate, an inner peripheral surface of each of the upper through-opening and the lower through-opening is provided. A covering member is attached to cover the portion adjacent to each of the upper through-opening and the lower through-opening on the back surface of the cathode plate and the anode plate and not covered by the gasket,
The electrolytic cell according to claim 6 or 7.
Each of the covering members has a tubular portion inserted into each of the upper through-opening or the lower through-opening and a flange portion projecting from the rear end of the tubular portion,
The electrolytic cell according to claim 8.
The cylindrical portion of the covering member has a cylindrical shape, and the upper opening, the upper through-opening, the upper communication opening, the lower opening, the lower through-opening, and the lower communication opening have a circular cross-sectional shape,
The inner diameters of the upper through-opening and the lower through-opening are larger than the inner diameters of the upper opening and the lower opening, respectively, by twice the thickness of the cylindrical portion of the covering member. the inner diameter is the same as the inner diameters of the upper opening and the lower opening;
The length of the cylindrical portion is the same as the thickness of the cathode plate,
The flange portion of the covering member has an annular shape, and the outer diameter of the flange portion is the same as the inner diameters of the upper communication opening and the lower communication opening,
The thickness of the flange portion is the same as the thickness of the gasket,
The electrolytic cell according to claim 9.
each of the covering members is made of a synthetic resin;
Electrolytic cell according to any one of claims 8 to 10.
Using the electrolytic cell according to any of claims 1 to 10, wherein at least one cation exchange membrane is arranged between the cathode plate and the anode plate, the quaternary ammonium salt A method for producing an aqueous quaternary ammonium hydroxide solution using an aqueous solution as a raw material.