WO2024009599A1

WO2024009599A1 - Electrolysis tank

Info

Publication number: WO2024009599A1
Application number: PCT/JP2023/017232
Authority: WO
Inventors: 秀成石丸; 裕史井上
Original assignee: 株式会社トクヤマ
Priority date: 2022-07-08
Filing date: 2023-05-08
Publication date: 2024-01-11
Also published as: TW202403106A; JP2024008512A

Abstract

This electrolysis tank, in which increase in electrolysis voltage is prevented and a stable operation of the electrolysis tank is ensured, comprises: a cathode frame body having a cathode plate fixed to an internal surface thereof; an anode frame body having an anode plate fixed to an internal surface thereof; an ion-exchange membrane disposed between the cathode frame body and the anode frame body; a cathode-side fluid supply channel for supplying a cathode-side fluid to a cathode chamber established between the cathode frame body and the ion-exchange membrane; and a cathode-side fluid discharge channel for discharging the cathode-side fluid from the cathode chamber; an anode-side fluid supply channel for supplying an anode-side fluid to an anode chamber established between the anode frame body and the ion-exchange membrane; and an anode-side fluid discharge channel for discharging the anode-side fluid from the anode chamber. The effective channel cross-sectional area CD of the cathode-side fluid discharge channel is larger than the effective channel cross-sectional area CS of the cathode-side fluid supply channel. The effective channel cross-sectional area AD of the anode-side fluid discharge channel is larger than the effective channel cross-sectional area AS of the anode-side fluid supply channel.

Description

電解槽electrolytic cell

　本発明は、電解槽、更に詳しくは、それに限定されるものではないが、第４級アンモニウム塩水溶液を原料として水酸化第４級アンモニウム水溶液を製造するのに好適に使用することができる電解槽に関する。 The present invention relates to an electrolytic cell, and more specifically, although not limited thereto, an electrolytic cell that can be suitably used to produce a quaternary ammonium hydroxide aqueous solution using a quaternary ammonium salt aqueous solution as a raw material. Regarding.

　下記特許文献１乃至４には、第４級アンモニウム塩水溶液を原料として水酸化第４級アンモニウム水溶液を製造する製造方法が開示されている。かような製造方法の実施には、陰極枠体とこの陰極枠体の内面に固定された陰極板と陽極枠体とこの陽極枠体の内面に固定された陽極板とを含む電解槽が使用される。陰極板と陽極板との間には少なくとも１個の陽イオン交換膜が配設されており、陰極枠体と陽イオン交換膜との間には陰極室が規定され、陽極枠体と陽イオン交換膜との間には陽極室が規定されている。そして、陰極室に陰極側流体を供給するための陰極側流体供給路及び陰極室から陰極側流体を排出するための陰極側流体排出路並びに陽極室に陽極側流体を供給するための陽極側流体供給路及び陽極室から陽極側流体を排出するための陽極側流体排出路が配設されている。更に詳しくは、陰極枠体には幅方向に間隔をおいて配置された複数個の上側開口から延びる複数個の上側流路及び幅方向に間隔をおいて配置された複数個の下側開口から延びる複数個の下側流路が配設されており、上側流路と下側流路との一方が上記陰極側流体排出路を構成し、上側流路と下側流路との他方が上記陰極側流体供給路を構成する。同様に陽極枠体には幅方向に間隔をおいて配置された複数個の上側開口から延びる複数個の上側流路及び幅方向に間隔をおいて配置された複数個の下側開口から延びる複数個の下側流路が配設されており、上側流路と下側流路との一方が上記陽極側流体排出路を構成し、上側流路と下側流路との他方が上記陽極側流体供給路を構成する。陰極側流体供給路、陰極室及び陰極側流体排出路を通して陰極側流体即ち水酸化第４級アンモニウム水溶液が循環され、陽極側流体供給路、陽極室及び陽極側流体排出路を通して陽極側流体即ち第４級アンモニウム塩水溶液が循環される。 Patent Documents 1 to 4 listed below disclose manufacturing methods for producing a quaternary ammonium hydroxide aqueous solution using a quaternary ammonium salt aqueous solution as a raw material. To implement such a manufacturing method, an electrolytic cell is used that includes 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. be done. At least one cation exchange membrane is disposed between the cathode plate and the anode plate, a cathode chamber is defined between the cathode frame and the cation exchange membrane, and a cathode chamber is defined between the anode frame and the cation exchange membrane. An anode chamber is defined between the exchange membrane and the exchange membrane. and a cathode side fluid supply path for supplying cathode side fluid to the cathode chamber, a cathode side fluid discharge path for discharging the cathode side fluid from the cathode chamber, and an anode side fluid for supplying the anode side fluid to the anode chamber. An anode side fluid discharge path is provided for discharging the anode side fluid from the supply path and the anode chamber. More specifically, the cathode frame has a plurality of upper passages extending from a plurality of upper openings arranged at intervals in the width direction and a plurality of lower openings extending from a plurality of lower openings arranged at intervals in the width direction. A plurality of extending lower channels are disposed, one of the upper channel and the lower channel forming the cathode side fluid discharge channel, and the other of the upper channel and the lower channel forming the cathode side fluid discharge channel. This constitutes a cathode side fluid supply path. Similarly, the anode frame has a plurality of upper channels extending from a plurality of upper openings arranged at intervals in the width direction and a plurality of channels extending from a plurality of lower openings arranged at intervals in the width direction. One of the upper and lower flow channels constitutes the anode side fluid discharge channel, and the other of the upper and lower flow channels constitutes the anode side fluid discharge channel. Configure a fluid supply path. The cathode side fluid, that is, the quaternary ammonium hydroxide aqueous solution is circulated through the cathode side fluid supply path, the cathode chamber, and the cathode side fluid discharge path, and the anode side fluid, that is, the anode side fluid is circulated through the anode side fluid supply path, the anode chamber, and the anode side fluid discharge path. The quaternary ammonium salt aqueous solution is circulated.

特開昭６２－１４２７９２号公報JP 62-142792 Publication 特公平８－１６２７４号公報Special Publication No. 8-16274 特公平８－１９５３９号公報Special Publication No. 8-19539 特開２００９－１３４７７号公報Japanese Patent Application Publication No. 2009-13477

　而して、上記のとおりの電解槽においては、陰極側流体供給路の有効流路断面積と陰極側流体排出路の有効流路断面積とを実質上同一に設定し、そしてまた陽極側流体供給路の有効流路断面積と陽極側流体排出路の有効流路断面積とを実質上同一に設定している。そして、特に特願２０２２－３３６５１において本発明者等が提案した形態の電解槽（即ち、陰極板の上端部には陰極枠体の上側開口に整合する少なくとも１個の上側貫通開口が形成されており、陰極板の下端部には陰極枠体の下側開口に整合する少なくとも１個の下側貫通開口が形成されており、陽極板の上端部には該陽極枠体の上側開口に整合する少なくとも１個の上側貫通開口が形成されており、陽極板の下端部には陽極枠体の該下側開口に整合する少なくとも１個の下側貫通開口が形成されており、陰極板に形成されている上側貫通開口及び下側貫通開口並びに陽極板に形成されている上側貫通開口及び下側貫通開口が流体流路の有効流路断面積を規定している形態の電解槽）においては、最大限の電界効率を達成するために有効流路面積を必要最小限に設定している。然るに、本発明者等は、電解槽の作動について鋭意検討及び実験を重ねた結果、陰極室及び陽極室においては電解作用に起因してガスが生成され、陰極側流体排出路及び陽極側流体排出路においては陰極側流体及び陽極側流体に加えて生成されたガスも流動されることに起因して、陰極側流体排出路及び陽極側流体排出路では陰極側流体供給路及び陽極側流体供給路に比べて流速が増大されて背圧が生成され、これに起因して電解電圧が上昇され電解槽の安定した作動が阻害される傾向があることを認識した。 In the electrolytic cell as described above, the effective flow cross-sectional area of the cathode-side fluid supply path and the effective flow cross-sectional area of the cathode-side fluid discharge path are set to be substantially the same, and the anode-side fluid The effective flow cross-sectional area of the supply path and the effective flow cross-sectional area of the anode side fluid discharge path are set to be substantially the same. In particular, an electrolytic cell of the form proposed by the present inventors in Japanese Patent Application No. 2022-33651 (that is, the upper end of the cathode plate is formed with at least one upper through-opening that matches the upper opening of the cathode frame). The lower end of the cathode plate is formed with at least one lower through-opening aligned with the lower opening of the cathode frame, and the upper end of the anode plate is formed with at least one lower through opening aligned with the upper opening of the anode frame. at least one upper through opening is formed in the anode plate, at least one lower through opening is formed in the lower end of the anode plate that aligns with the lower opening in the anode frame; In an electrolytic cell in which the upper through opening and lower through opening formed in the anode plate and the upper through opening and lower through opening formed in the anode plate define the effective flow cross-sectional area of the fluid flow path, the maximum The effective channel area is set to the minimum necessary to achieve the highest electric field efficiency. However, as a result of extensive studies and experiments on the operation of electrolytic cells, the inventors have found that gas is generated in the cathode chamber and anode chamber due to electrolytic action, and the cathode side fluid discharge path and anode side fluid discharge path Due to the fact that in addition to the cathode side fluid and the anode side fluid, the generated gas is also flowed in the cathode side fluid discharge passage and the anode side fluid discharge passage, the cathode side fluid supply passage and the anode side fluid supply passage are It has been recognized that the flow rate is increased compared to that of the electrolytic cell, and a back pressure is generated, which tends to increase the electrolysis voltage and impede stable operation of the electrolytic cell.

　本発明は上記事実に鑑みてなされたものであり、その主たる技術的課題は、電解電圧の上昇が回避され電解槽の安定した作動が確保される新規且つ改良された電解槽を提供することである。 The present invention has been made in view of the above facts, and its main technical problem is to provide a new and improved electrolytic cell that avoids an increase in electrolytic voltage and ensures stable operation of the electrolytic cell. be.

　本発明者等は、本発明者等が認識した上記のとおりの事実を踏まえ、陰極側流体排出路の有効流路断面積ＣＤを陰極側流体供給路の有効流路断面積ＣＳよりも大きくし、そしてまた陽極側流体排出路の有効流路断面積ＡＤを陽極側流体供給路の有効流路断面積ＡＳよりも大きくすることによって、上記主たる技術的課題を達成することができることを見出した。 Based on the above-mentioned facts recognized by the inventors, the inventors have made the effective channel cross-sectional area CD of the cathode-side fluid discharge channel larger than the effective channel cross-sectional area CS of the cathode-side fluid supply channel. We have also found that the above main technical problem can be achieved by making the effective flow cross-sectional area AD of the anode-side fluid discharge path larger than the effective flow cross-sectional area AS of the anode-side fluid supply path.

　即ち、本発明によれば、上記主たる技術的課題を達成する電解槽として、
　内面に陰極板が固定された陰極枠体と、内面に陽極板が固定された陽極枠体と、該陰極枠体と該陽極枠体との間に配設されたイオン交換膜と、該陰極枠体と該イオン交換膜との間に規定された陰極室に陰極側流体を供給するための陰極側流体供給路と、該陰極室から陰極側流体を排出するための陰極側流体排出路と、該陽極枠体と該イオン交換膜との間に規定された陽極室に陽極側流体を供給するための陽極側流体供給路と、該陽極室から陽極側流体を排出するための陽極側流体排出路とを含む電解槽において、
　該陰極側流体排出路の有効流路断面積ＣＤは該陰極側流体供給路の有効流路断面積ＣＳよりも大きく、該陽極側流体排出路の有効流路断面積ＡＤは該陽極側流体供給路の有効流路断面積ＡＳよりも大きい、
　ことを特徴とする電解槽が提供される。 That is, according to the present invention, as an electrolytic cell that achieves the above main technical problem,
A cathode frame having a cathode plate fixed to its inner surface, an anode frame having an anode plate fixed to its inner surface, an ion exchange membrane disposed between the cathode frame and the anode frame, and the cathode. a cathode side fluid supply path for supplying a cathode side fluid to a cathode chamber defined between the frame and the ion exchange membrane; and a cathode side fluid discharge path for discharging the cathode side fluid from the cathode chamber. , an anode side fluid supply path for supplying an anode side fluid to an anode chamber defined between the anode frame and the ion exchange membrane, and an anode side fluid for discharging the anode side fluid from the anode chamber. In an electrolytic cell including a discharge path,
The effective passage cross-sectional area CD of the cathode-side fluid discharge passage is larger than the effective passage cross-sectional area CS of the cathode-side fluid supply passage, and the effective passage cross-sectional area AD of the anode-side fluid discharge passage is larger than the effective passage cross-sectional area CS of the cathode-side fluid supply passage. larger than the effective flow cross-sectional area AS of the channel,
An electrolytic cell is provided.

　該有効流路断面積ＣＤは該有効流路断面積ＣＳの１．１乃至３．０倍（ＣＤ＝１．１乃至３．０ＣＳ）であり、該有効流路断面積ＡＤは該有効流路断面積ＡＳの１．１乃至３．０倍（ＡＤ＝１．１乃至３．０ＡＳ）である、特に該有効流路断面積ＣＤは該有効流路断面積ＣＳの１．５乃至２．５倍（ＣＤ＝１．５乃至２．５ＣＳ）であり、該有効流路断面積ＡＤは該有効流路断面積ＡＳの１．５乃至２．５倍（ＡＤ＝１．５乃至２．５ＡＳ）である、のが好ましい。 The effective channel cross-sectional area CD is 1.1 to 3.0 times the effective channel cross-sectional area CS (CD=1.1 to 3.0 CS), and the effective channel cross-sectional area AD is 1.1 to 3.0 times the effective channel cross-sectional area CS. The effective channel cross-sectional area CD is 1.1 to 3.0 times the cross-sectional area AS (AD=1.1 to 3.0 AS), particularly the effective channel cross-sectional area CD is 1.5 to 2.5 times the effective channel cross-sectional area CS. (CD=1.5 to 2.5CS), and the effective flow path cross-sectional area AD is 1.5 to 2.5 times the effective flow path cross-sectional area AS (AD=1.5 to 2.5AS). It is preferable that

　好適実施形態においては、
　該陰極枠体には、該内面の上端部に位置する上側開口から延びる少なくとも１個の上側流路及び該内面の下端部に位置する下側開口から延びる少なくとも１個の下側流路が配設されており、
　該陽極枠体には、該内面の上端部に位置する上側開口から延びる少なくとも１個の上側流路及び該内面の下端部に位置する下側開口から延びる少なくとも１個の下側流路が配設されており、
　該陰極板は該陰極枠体の該上側開口よりも上方から該陰極枠体の該下側開口よりも下方まで連続して延在し、
　該陰極板の上端部には該陰極枠体の該上側開口に整合する少なくとも１個の上側貫通開口が形成されており、該陰極板の下端部には該陰極枠体の該下側開口に整合する少なくとも１個の下側貫通開口が形成されており、
　該陽極板は該陽極枠体の該上側開口よりも上方から該陽極枠体の該下側開口よりも下方まで連続して延在し、
　該陽極板の上端部には該陽極枠体の該上側開口に整合する少なくとも１個の上側貫通開口が形成されており、該陽極板の下端部には該陽極枠体の該下側開口に整合する少なくとも１個の下側貫通開口が形成されており、
　該陰極板の該上側貫通開口及び該陰極枠体の該上側流路が該陰極側流体排出路と該陰極側流体供給路との一方を構成し、該陰極板の該下側貫通開口及び該陰極枠体の該下側流路が該陰極側流体排出路と該陰極側流体供給路との他方を構成し、
　該陽極板の該上側貫通開口及び該陽極枠体の該上側流路が該陽極側流体排出路と該陽極側流体供給路との一方を構成し、該陽極板の該下側貫通開口及び該陽極枠体の該下側流路が該陽極側流体排出路と該陽極側流体供給路との他方を構成する。 In a preferred embodiment,
The cathode frame is provided with at least one upper channel extending from an upper opening located at an upper end of the inner surface and at least one lower channel extending from a lower opening located at a lower end of the inner surface. has been established,
The anode frame has at least one upper channel extending from an upper opening located at an upper end of the inner surface and at least one lower channel extending from a lower opening located at a lower end of the inner surface. has been established,
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 at least one upper through opening aligned with the upper opening of the cathode frame. at least one lower through opening is formed in alignment;
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 at least one upper through opening aligned with the upper opening of the anode frame. at least one lower through opening is formed in alignment;
The upper through-opening of the cathode plate and the upper passage of the cathode frame constitute one of the cathode-side fluid discharge passage and the cathode-side fluid supply passage; The lower flow path of the cathode frame constitutes the other of the cathode fluid discharge path and the cathode fluid supply path,
The upper through-opening of the anode plate and the upper passage of the anode frame constitute one of the anode-side fluid discharge passage and the anode-side fluid supply passage; The lower flow path of the anode frame constitutes the other of the anode side fluid discharge path and the anode side fluid supply path.

　好ましくは、該陰極枠体には、該内面の上端部に幅方向に間隔をおいて配置された複数個の上側開口から延びる複数個の上側流路及び該内面の下端部に幅方向に間隔をおいて配置された複数個の下側開口から延びる複数個の下側流路が配設されており、
　該陽極枠体には、該内面の上端部に幅方向に間隔をおいて配置された複数個の上側開口から延びる複数個の上側流路及び該内面の下端部に幅方向に間隔をおいて配置された複数個の下側開口から延びる複数個の下側流路が配設されており、
　該陰極板の上端部には該陰極枠体の該複数個の上側開口の各々に夫々整合する複数個の上側貫通開口が形成されており、該陰極板の下端部には該陰極枠体の該複数個の下側開口の各々に夫々整合する複数個の下側貫通開口が形成されており、
　該陽極板の上端部には該陽極枠体の該複数個の上側開口の各々に夫々整合する複数個の上側貫通開口が形成されており、該陽極板の下端部には該陽極枠体の該複数個の下側開口の各々に夫々整合する複数個の下側貫通開口が形成されており、
　該陰極側流体排出路を構成する該陰極板の該上側貫通開口及び該陰極枠体の該上側流路又は該陰極板の該下側貫通開口及び該陰極枠体の該下側流路の数は、該陰極側流体供給路を構成する該陰極板の該下側貫通開口及び該陰極枠体の該下側流路又は該陰極板の該上側貫通開口及び該陰極枠体の該上側流路の数よりも多く、
　該陽極側流体排出路を構成する該陽極板の該上側貫通開口及び該陽極枠体の該上側流路又は該陽極板の該下側貫通開口及び該陽極枠体の該下側流路の数は、該陽極側流体供給路を構成する該陽極板の該下側貫通開口及び該陽極枠体の該下側流路又は該陽極板の該上側貫通開口及び該陽極枠体の該上側流路の数よりも多い。 Preferably, the cathode frame has a plurality of upper passages extending from a plurality of upper openings spaced apart in the width direction at an upper end of the inner surface, and a plurality of upper channels spaced apart in the width direction at a lower end of the inner surface. A plurality of lower flow passages extending from a plurality of lower openings arranged at intervals are arranged,
The anode frame includes a plurality of upper channels extending from a plurality of upper openings arranged at intervals in the width direction at an upper end of the inner surface, and a plurality of upper channels extending at intervals in the width direction at a lower end of the inner surface. A plurality of lower flow passages extending from the plurality of lower openings are arranged,
A plurality of upper through-openings are formed at the upper end of the cathode plate, each of which aligns with each of the upper openings of the cathode frame, and a lower end of the cathode plate is formed with a plurality of upper through openings that are aligned with each of the plurality of upper openings of the cathode frame. A plurality of lower through openings are formed that respectively align with each of the plurality of lower openings,
A plurality of upper through openings are formed at the upper end of the anode plate, each of which aligns with each of the upper openings of the anode frame, and a lower end of the anode plate is formed with a plurality of upper through openings that are aligned with each of the upper openings of the anode frame. A plurality of lower through openings are formed that respectively align with each of the plurality of lower openings,
The number of the upper through-opening of the cathode plate and the upper flow path of the cathode frame or the lower through-opening of the cathode plate and the lower flow path of the cathode frame that constitute the cathode side fluid discharge path. is the lower through-opening of the cathode plate and the lower channel of the cathode frame, or the upper through-opening of the cathode plate and the upper channel of the cathode frame, which constitute the cathode-side fluid supply channel; more than the number of
The number of the upper through-opening of the anode plate and the upper flow path of the anode frame or the lower through-opening of the anode plate and the lower flow path of the anode frame that constitute the anode side fluid discharge path. is the lower through-opening of the anode plate and the lower flow path of the anode frame, or the upper through-opening of the anode plate and the upper flow path of the anode frame, which constitute the anode-side fluid supply path; more than the number of

　該陰極枠体の該上側開口及び該下側開口並びに該陰極板の該上側貫通開口及び該下側貫通開口は円形断面形状を有し、該陽極枠体の該上側開口及び該下側開口並びに該陽極板の該上側貫通開口及び該下側貫通開口は円形断面形状を有するのが好都合である。該陰極板及び該陽極板は矩形板から構成されているのが望ましい。 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, and the upper opening and the lower opening of the anode frame and Advantageously, the upper through-opening and the lower through-opening of the anode plate have a circular cross-sectional shape. Preferably, the cathode plate and the anode plate are rectangular plates.

　本発明の好適形態においては、上述したとおりの電解槽において該陰極板と該陽極板との間に少なくとも１個の陽イオン交換膜を配置し、かかる電解槽を使用して第４級アンモニウム塩水溶液を原料として水酸化第４級アンモニウム水溶液を製造する。 In a preferred form of the invention, at least one cation exchange membrane is disposed between the cathode plate and the anode plate in an electrolytic cell as described above, and such electrolytic cell is used to produce a quaternary ammonium salt. A quaternary ammonium hydroxide aqueous solution is produced using an aqueous solution as a raw material.

　本発明の電解槽においては、陰極側流体排出路の有効流路断面積ＣＤは陰極側流体供給路の有効流路断面積ＣＳよりも大きく、陽極側流体排出路の有効流路断面積ＡＤは陽極側流体供給路の有効流路断面積ＡＳよりも大きい故に、後述する実施例からも明確に理解されるとおり、電解電圧の上昇が回避され電解槽の安定した作動が確保される。 In the electrolytic cell of the present invention, the effective passage cross-sectional area CD of the cathode side fluid discharge passage is larger than the effective passage cross-sectional area CS of the cathode side fluid supply passage, and the effective passage cross-sectional area AD of the anode side fluid discharge passage is Since it is larger than the effective passage cross-sectional area AS of the anode side fluid supply passage, as will be clearly understood from the examples described later, an increase in electrolytic voltage is avoided and stable operation of the electrolytic cell is ensured.

本発明に従って構成された電解槽の好適実施形態を示す簡略断面図。1 is a simplified cross-sectional view showing a preferred embodiment of an electrolytic cell constructed according to the present invention. 図１に示す電解槽における陰極枠体及び陰極板を示す、図１の線II－IIに沿った簡略断面図。2 is a simplified cross-sectional view taken along line II-II in FIG. 1, showing a cathode frame and a cathode plate in the electrolytic cell shown in FIG. 1. FIG. 図１に示す電解槽における陰極枠体上側開口、陰極板に形成されている上側貫通開口及びガスケットに形成されている上側連通開口を示す部分拡大断面図。FIG. 2 is a partially enlarged cross-sectional view showing an upper opening of the cathode frame, an upper through-hole formed in the cathode plate, and an upper communication opening formed in the gasket in the electrolytic cell shown in FIG. 1; 本発明に従って構成された電解槽の変形例における陰極枠体及び陰極板を示す、図２と同様の間の簡略断面図。FIG. 3 is a simplified cross-sectional view similar to FIG. 2 showing a cathode frame and a cathode plate in a modified example of an electrolytic cell constructed according to the present invention.

　以下、本発明に従って構成された電解槽の好適実施形態を図示している添付図面を参照して、更に詳細する。 Further details will now be given with reference to the accompanying drawings, which illustrate preferred embodiments of an electrolytic cell constructed in accordance with the present invention.

　図１及び図２を参照して説明すると、本発明に従って構成された図示の電解槽は、陰極枠体４（図１）、陽極枠体６（図１）、陰極側上壁部材８、陽極側上壁部材１０、陰極側下壁部材１２、陽極側下壁部材１４、陰極側前壁部材１６（図２）、陽極側前壁部材（図示していない）、陰極側後壁部材１８（図２）及び陽極側後壁部材（図示していない）によって構成された、中空直方体形状のハウジング２を含んでいる。陰極枠体４、陽極枠体６、陰極側前壁部材１６、陽極側前壁部材、陰極側後壁部材１８及び陽極側後壁部材は実質上垂直に延在し、陰極側上壁部材８、陽極側上壁部材１０、陰極側下壁部材１２及び陽極側下壁部材１４は実質上水平に延在している。陰極側上壁部材８の基端面（図１において右端面）は、締結ねじ或いは接着剤の如き適宜の連結手段によって陰極枠体４の内面上端縁部に連結され、陰極側下壁部材１２の基端面（図１において右端面）は適宜の連結手段によって陰極枠体４の内面下端縁部に連結されている。同様に、陽極側上壁部材１０の基端面（図１において左端面）は、適宜の連結手段によって陽極枠体６の内面上端縁部に連結され、陽極側下壁部材１４の基端面（図１において左端面）は適宜の連結手段によって陽極枠体６の内面下端縁部に連結されている。陰極側前壁部材１６は陰極枠体４の前面に、陽極側前壁部材は陽極枠体６の前面に、適宜の連結手段によって連結され、陰極側後壁部材１８は陰極枠体４の後面に、陽極側後壁部材は陽極枠体６の後面に、適宜の連結手段によって連結されている。陰極側及び陽極側の各々の上壁部材８及び１０、下壁部材１２及び１４、並びに前壁部材１６及び後壁部材１８は、上記のとおり陰極枠体４又は陽極枠体６に連結することに代えて、これら壁部材をあらかじめ一体に形成して、陰極枠体４又は陽極枠体６に連結することもできる。また、陰極枠体４又は陽極枠体６に壁部を一体に形成することもできる。更に、上壁部材８及び１０、下壁部材１２及び１４、並びに前壁部材１６及び後壁部材１８を一体に形成した場合は、陰極枠体４又は陽極枠体６にシール部材を介在させて固定することもできる。シール部材としては、後述するガスケット３８を陰極板３２又は陽極板５６に対応するサイズから陰極枠体４又は陽極枠体６に対応するサイズまで延在させて、延長部を利用することもできる。陰極枠体４、陽極枠体６、陰極側上壁部材８、陽極側上壁部材１０、陰極側下壁部材１２、陽極側下壁部材１４、陰極側前壁部材１６、陽極側前壁部材、陰極側後壁部材１８及び陽極側後壁部材は、後述する開口及び流路を除いて中実ブロック乃至板形態でよく、ポリプロピレン及びポリエチレンの如きオレフィン系樹脂、塩化ビニル系樹脂並びにフッソ系樹脂の如き適宜の合成樹脂から形成することができる。陰極枠体４、陽極枠体６、陰極側上壁部材８、陽極側上壁部材１０、陰極側下壁部材１２、陽極側下壁部材１４、陰極側前壁部材１６、陽極側前壁部材、陰極側後壁部材１８及び陽極側後壁部材の相互連結部位間にはガスケットの如き適宜の密封部材（図示していない）を介在在させることができる。 Referring to FIGS. 1 and 2, the illustrated electrolytic cell constructed according to 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 housing 2 has a hollow rectangular parallelepiped shape. The cathode frame 4, the anode frame 6, the cathode front wall member 16, the anode front wall member, the cathode rear wall member 18, and the anode rear wall member extend substantially vertically, and the cathode upper wall member 8 , 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 inner surface upper end edge of the cathode frame 4 by a suitable connecting means such as a fastening screw or an adhesive, and 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 appropriate connecting means. Similarly, the proximal end surface (left end surface in FIG. 1) of the anode side upper wall member 10 is connected to the inner surface upper end edge of the anode frame 6 by appropriate connecting means, and the proximal end surface (the left end surface in FIG. 1) is connected to the lower edge of the inner surface of the anode frame 6 by a suitable 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 by appropriate connecting means, and the cathode side rear wall member 18 is connected to the rear surface of the cathode frame 4. In addition, the anode side rear wall member is connected to the rear surface of the anode frame 6 by suitable connection means. 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 on the cathode side and the anode side 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. Further, the wall portion can also 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, and the front wall member 16 and 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 portion can also 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 upper wall member 8, anode upper wall member 10, cathode lower wall member 12, anode lower wall member 14, cathode front wall member 16, anode front wall member The cathode-side rear wall member 18 and the anode-side rear wall member may be in the form of a solid block or a plate, except for the openings and channels described below, and may be made of olefin resins such as polypropylene and polyethylene, vinyl chloride resins, and fluorocarbon resins. It can be formed from an appropriate synthetic resin such as. Cathode frame 4, anode frame 6, cathode upper wall member 8, anode upper wall member 10, cathode lower wall member 12, anode lower wall member 14, cathode front wall member 16, anode front wall member A suitable sealing member (not shown), such as a gasket, may be interposed between the interconnection portions of the cathode-side rear wall member 18 and the anode-side rear wall member.

　図１及び図２と共に図３を参照して説明を続けると、上記陰極枠体４の内面（図１において左側面）の上端部には幅方向（図１において紙面に垂直な方向、図２において左右方向）に等間隔をおいて複数個（図示の場合は６個）の上側開口２０（図１及び図３にそのうちの１個を夫々破線及び実線で図示している）が形成され、そして陰極枠体４には上側開口２０の各々から実質上水平に陰極枠体４を貫通して延びる複数個（図示の場合は６個）の上側流路２２（図１及び図３にそのうちの１個を夫々破線及び実線で図示している）が形成されている。同様に、上記陰極枠体４の内面（図１において左側面）の下端部には幅方向（図１において紙面に垂直な方向、図２において左右方向）に等間隔をおいて複数個（図示の場合は３個）の下側開口２４（図１にそのうちの１個を破線で図示している）が形成され、そして陰極枠体４には下側開口２４の各々から実質上水平に陰極枠体４を貫通して延びる複数個（図示の場合は３個）の下側流路２６（図１にそのうちの１個を破線で図示している）が形成されている。上側開口２０及び下側開口２４は円形でよく、上側流路２２の横断面形状及び下側流路２６の横断面形状は上側開口２０及び下側開口２４の円形に合致した円形でよい。上流流路２２と下流流路２６とは、ハウジング２の外側に配設されている外側流路（図示していない）によって接続されており、外側流路３１（図２にその一部を図示している）には循環用ポンプ、製品貯蔵用タンク及び流動制御のための複数個の弁部材等も配設されている（外側流路及びこれに配設された上記のとおりの構成要素は当業者には周知であるので、これらについての詳細な説明は本明細書においては省略する）。 Continuing the explanation with reference to FIG. 3 together with FIGS. 1 and 2, the upper end of the inner surface (the left side in FIG. 1) of the cathode frame 4 has a width direction (direction perpendicular to the plane of the paper in FIG. A plurality of (six 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 left-right direction), The cathode frame 4 has a plurality of (six in the illustrated case) upper channels 22 (one of which is shown in FIGS. 1 and 3) extending substantially horizontally through the cathode frame 4 from each of the upper openings 20. (one shown by a broken line and one by a solid line, respectively) are formed. Similarly, on the lower end of the inner surface (left side surface in FIG. 1) of the cathode frame 4, there are a plurality of electrodes (not shown) spaced equally apart in the width direction (direction perpendicular to the page in FIG. 1, horizontal direction in FIG. 2). In this case, three lower openings 24 (one of which is indicated by a broken line in FIG. 1) are formed in the cathode frame 4, and the cathode is inserted substantially horizontally from each of the lower openings 24 into the cathode frame 4. A plurality (three in the illustrated case) of lower flow channels 26 (one of which is shown by a broken line in FIG. 1) extending through the frame 4 is formed. The upper opening 20 and the lower opening 24 may be circular, and the cross-sectional shape of the upper flow path 22 and the cross-sectional shape of the lower flow path 26 may be circular, matching the circular shapes of the upper opening 20 and the lower opening 24. The upstream flow path 22 and the downstream flow path 26 are connected by an outer flow path (not shown) disposed outside the housing 2, and an outer flow path 31 (part of which is shown in FIG. 2). (shown) is also equipped with a circulation pump, a product storage tank, and multiple valve members for flow control (the outer flow path and the above-mentioned components arranged therein are As these are well known to those skilled in the art, detailed explanations thereof are omitted here).

　陰極枠体４の内面には陰極板３２が固定されている。図示の実施形態においては、陰極板３２は陰極枠体４に形成されている上記上側開口２０よりも上方から陰極枠体４に形成されている上記下側開口２４よりも下方まで連続して延在している。陰極板３２はニッケルの如き適宜の導電性金属から形成された矩形板から構成されており、その上端面は上記陰極側上壁部材８の内面（即ち下面）に当接乃至近接し、その下端面は上記陰極側下壁部材１２の内面（即ち上面）に当接乃至近接し、その前側面は前壁部材１６の内面（即ち後面）に当接乃至近接し、その後側面は上記後壁部材１８の内面（即ち前面）に当接乃至近接している。陰極枠体４に対する陰極板３２の固定は、例えば陰極板３２の４角部において陰極板３２を通して締結ねじ（図示していない）を陰極枠体４に螺着することによって好都合に実施することができる。陰極板３２の上端部には幅方向（図１において紙面に垂直な方向、図２において左右方向）に等間隔をおいて複数個（図示の場合は６個）の上側貫通開口３４が形成され、陰極板３２の下端部には幅方向（図１において紙面に垂直な方向、図２において左右方向）に等間隔をおいて複数個（図示の場合は３個）の下側貫通開口３６が形成されている（上側貫通開口３４及び下側貫通開口３６については後に更に言及する）。陰極板３２に形成されている上側貫通開口３４の各々は陰極枠体４の上端部に形成されている上記上側開口２０の各々に夫々整合して位置している。図示の実施形態においては、上側貫通開口３４の各々は上記上側開口２０の各々と同一形状（従って円形）で且つ同一寸法である。同様に、陰極板３２に形成されている下側貫通開口３６の各々は陰極枠体４の下端部に形成されている上記下側開口２４の各々に夫々整合して位置していることが重要である。図示の実施形態においては、下側貫通開口３６の各々は上記下側開口２４の各々と同一形状（従って円形）で且つ同一寸法である。上側貫通開口３４（及び上側開口２０）は陰極板３２の上端に近接して位置し、下側貫通開口３６（及び下側開口２４）は陰極板３２の下端に近接して位置するのが好ましい。 A cathode plate 32 is fixed to the inner surface of the cathode frame 4. In the illustrated embodiment, the cathode plate 32 extends continuously from above the upper opening 20 formed in the cathode frame 4 to below the lower opening 24 formed in the cathode frame 4. There is. The cathode plate 32 is composed of a rectangular plate made of a suitable conductive metal such as nickel, and its upper end surface is in contact with or close to the inner surface (i.e., lower surface) of the cathode side upper wall member 8, and The end surface is in contact with or close to the inner surface (i.e., the upper surface) of the cathode side lower wall member 12, the front surface thereof is in contact with or close to the inner surface (i.e., the rear surface) of the front wall member 16, and the rear surface is in contact with or close to the inner surface (i.e., the rear surface) of the cathode side lower wall member 12. It is in contact with or close to the inner surface (i.e., front surface) of 18. The fixation of the cathode plate 32 to the cathode frame 4 can be conveniently carried out, for example, by 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. A plurality of (six in the illustrated case) upper through openings 34 are formed at the upper end of the cathode plate 32 at equal intervals in the width direction (perpendicular to the plane of the paper in FIG. 1, horizontal direction in FIG. 2). , a plurality (three in the illustrated case) of lower through-openings 36 are provided at the lower end of the cathode plate 32 at equal intervals in the width direction (direction perpendicular to the plane of the paper in FIG. 1, horizontal direction in FIG. 2). (The upper through opening 34 and the lower through opening 36 will be further referred to later). Each of the upper through openings 34 formed in the cathode plate 32 is positioned in alignment with each of the upper openings 20 formed at the upper end of the cathode frame 4. 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 positioned in alignment with each of the lower openings 24 formed in the lower end of the cathode frame 4. It 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. Preferably, upper through opening 34 (and upper opening 20) is located proximate the upper end of cathode plate 32, and lower through opening 36 (and lower opening 24) is located proximate the lower end of cathode plate 32. .

　図１と共に図３を参照して説明を続けると、陰極枠体４と陰極板３２との間にはガスケット３８が介在されているのが好適である。ガスケット３８によって陰極板３２を陰極枠体４に安定して固定することができ、そしてまた陰極枠体４と陰極板３２との界面への液体の浸透による腐食等を防止することができる。このガスケット３８は陰極板３２と実質上同一寸法の矩形板でよく（前述した如くガスケット３８を陰極枠体４に対応した大きさにすることもできる）、適宜のエラストマ、例えばシリコーンゴム、エチレンプロピレンゴム、クロロプレンゴム、軟質塩化ビニル、ブチルゴム、ブタジエンゴム又はフッ素ゴムから形成することができる。陰極枠体４と陰極板３２との間にガスケット３８を介在させる場合には、陰極板３２の４角部において陰極板３２と共にガスケット３８を通して締結ねじ（図示していない）を陰極枠体４に螺着することができる。ガスケット３８の上端部には、陰極板３２に形成されている上側貫通開口３４の各々と陰極枠体４に形成されている上側開口２０の各々とを連通する複数個（図示の場合は６個の上側連通開口４０が形成され、ガスケット３８の下端部には、陰極板３２に形成されている下側貫通開口３６の各々と陰極枠体４に形成されている下側開口２４の各々とを連通する複数個（図示の場合は３個）の下側連通開口４２が形成されている。図３を参照することによって明確に理解される如く、ガスケット３８に形成される上側連通開口４０及び下側連通開口４２は、上側貫通開口３４及び上側開口２０並びに下側貫通開口３６及び下側開口２４よりも大きいことが望ましい。ガスケット３８に形成される上側連通開口４０及び下側連通開口４２が上側貫通開口３４及び上側開口２０並びに下側貫通開口３６及び下側開口２４と実質上同一寸法である場合には、電解槽を連続して作動させると、ガスケット３８が幾分膨張されて上側連通開口４０及び下側連通開口４２が縮小及び変位され、これに起因して上側貫通開口３４と上側開口２０との連通並びに下側貫通開口３６と下側開口２４との連通が不充分になる或いは毀損されてしまう傾向がある。上側連通開口４０及び下側連通開口４２は、上側貫通開口３４及び上側開口２０並びに下側貫通開口３６及び下側開口２４の直径よりも所定長さ大きい直径を有する円形でよい。上側連通開口４０及び下側連通開口４２の各々は、必ずしも上側貫通開口３４及び上側開口２０並びに下側貫通開口３６及び下側開口２４の各々と同心である必要はなく偏心させることもできる。上側連通開口４０及び下側連通開口４２の直径並びに上側貫通開口３４及び上側開口２０並びに下側貫通開口３６及び下側開口２４に対する偏心度合いは、電解槽の連続的作動によるガスケット３８の膨張及び変位に基いて実験的に設定することができる。ガスケット３８に形成される上側連通開口４０及び下側連通開口４２を大きくする程、連通が不充分になる或いは毀損される可能性は低くなるが、後述する如く陰極板３２の裏面に液が触れる面積が増大することで、電食乃至腐食が発生し、液中に混入する電極金属が増加してしまう。このため、ガスケット３８に形成される上側連通開口４０及び下側連通開口４２としての好ましいサイズは、上側貫通開口３４及び上側開口２０並びに下側貫通開口３６及び下側開口２４のサイズの＋３０ｍｍ以下、好ましくは＋２０ｍｍ以下、より好ましくは＋１０ｍｍ以下である。また、ガスケット３８に膨張しにくい材質を用いれば、上側連通開口４０及び下側連通開口４２のサイズが上側貫通開口３４及び上側開口２０並びに下側貫通開口３６及び下側開口２４のサイズに近い場合でも連通が不充分になる或いは毀損される可能性は低くなる。そのため、ガスケット３８に使用する材質としては、線膨張係数が好ましくは３×１０^－４（１／℃）以下、より好ましくは１．５×１０^－４（１／℃）以下、最も好ましくは１×１０^－４（１／℃）以下である。 Continuing the description with reference to FIG. 3 together with FIG. 1, it is preferable that a gasket 38 be interposed between the cathode frame 4 and the cathode plate 32. The gasket 38 allows the cathode plate 32 to be stably fixed to the cathode frame 4, and also prevents corrosion caused by liquid penetration into the interface between the cathode frame 4 and the cathode plate 32. 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 be sized to correspond to the cathode frame 4), and may be made of a suitable 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 inserted into 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, there are a plurality of holes (six in the illustrated case) that 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. An upper communication opening 40 is formed at the lower end of the gasket 38 to connect 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 lower communication openings 42 are formed in communication with each other.As will be more clearly understood by referring to FIG. It is desirable that the side communication opening 42 is larger than the upper side through-opening 34 and the upper side opening 20 and the lower side through-hole 36 and the lower side opening 24.The upper side communication opening 40 and the lower side communication opening 42 formed in the gasket 38 are If the through-opening 34 and the upper opening 20 and the lower through-opening 36 and the lower opening 24 are of substantially the same dimensions, the gasket 38 will expand somewhat to open the upper communicating opening as the electrolytic cell continues to operate. 40 and the lower communication opening 42 are reduced and displaced, and as a result, the communication between the upper through opening 34 and the upper opening 20 and the communication between the lower through opening 36 and the lower opening 24 become insufficient or damaged. The upper communication opening 40 and the lower communication opening 42 have a circular shape having a diameter that is larger by a predetermined length than the diameters of the upper through-hole 34 and the upper opening 20 and the lower through-opening 36 and the lower opening 24. Each of the upper communication opening 40 and the lower communication opening 42 does not necessarily have to be concentric with each of the upper through-hole 34 and the upper opening 20 and the lower through-opening 36 and the lower opening 24, and may be eccentric. The diameters of the upper communication opening 40 and the lower communication opening 42 and the eccentricity relative to the upper through opening 34 and the upper opening 20 and the lower through opening 36 and the lower opening 24 are determined by the expansion of the gasket 38 due to continuous operation of the electrolytic cell. The larger the upper communication opening 40 and lower communication opening 42 formed in the gasket 38, the lower the possibility that the communication will be insufficient or damaged. However, as will be described later, as the area in contact with the liquid increases on the back surface of the cathode plate 32, electrolytic corrosion or corrosion occurs, and the amount of electrode metal mixed into the liquid increases. The preferred size of the upper communication opening 40 and lower communication opening 42 is the size of the upper through-hole 34 and upper opening 20 and the lower through-opening 36 and lower opening 24 +30 mm or less, preferably +20 mm or less, more preferably +10 mm or less. Furthermore, if a material that does not easily expand is used for the gasket 38, the size of the upper communication opening 40 and the lower communication opening 42 is close to the size of the upper through-hole 34 and the upper opening 20, and the lower through-opening 36 and the lower opening 24. However, the possibility that communication will become insufficient or damaged will be reduced. Therefore, the material used for the gasket 38 should preferably have a coefficient of linear expansion of 3×10 ⁻⁴ (1/°C) or less, more preferably 1.5×10 ⁻⁴ (1/°C) or less, and most preferably 1/°C or less. ×10 ⁻⁴ (1/°C) or less.

　図示の実施形態においては、陽極枠体６は上述した陰極枠体４と実質上同一である。更に詳しくは、陰極枠体４と陽極枠体６とは両者間を図１において紙面に垂直に延びる仮想面を対称面とする面対称をなす。従って、陽極枠体６には、上側開口４４、上側流路４６、下側開口４８及び下側流路５０が配設されている。説明の重複を避けるため、上側開口４４、上側流路４６、下側開口４８及び下側流路５０の詳細な説明は省略する。上側流路４６と下側流路５０とはハウジング２の外側に配設されている外側流路（図示していない）によって接続されており、外側流路には循環用ポンプ、原料貯蔵用タンク及び流動制御のための複数個の弁部材等も配設されている（外側流路及びこれに配設された上記のとおりの構成要素は当業者には周知であるので、これらについての詳細な説明は本明細書においては省略する）。 In the illustrated embodiment, the anode frame 6 is substantially identical to the cathode frame 4 described above. More specifically, the cathode frame 4 and the anode frame 6 have plane symmetry between them with a virtual plane extending perpendicularly to the plane of the paper in FIG. 1 as a plane of symmetry. Therefore, the anode frame 6 is provided with an upper opening 44, an upper channel 46, a lower opening 48, and a lower channel 50. In order to avoid duplication of explanation, detailed explanations of the upper opening 44, the upper channel 46, the lower opening 48, and the lower channel 50 will be 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 etc. for flow control are also arranged (the outer flow path and the above-mentioned components arranged therein are well known to those skilled in the art, so detailed descriptions thereof will not be provided). (Description is omitted in this specification).

　陽極枠体６の内面には陽極板５６が固定されている。図示の実施形態において、陽極板５６は、陽極に適した適宜の導電性金属、例えば表面に酸化インジウムをメッキしたチタン、から形成されている点を除き、上述した陰極板３２と実質上同一である。更に詳しくは、陰極板３２と陽極板５６とは両者間を図１において紙面に垂直に延びる仮想面を対称面とする面対称をなす。従って、陽極板５６は陽極枠体６に形成されている上記上側開口４４よりも上方から陽極枠体６に形成されている上記下側開口４８よりも下方まで連続して延在する矩形状である。そして、陽極板５６には、陽極枠体６に形成されている上側開口４４及び下側開口４８に夫々に整合して位置する上側貫通開口５８及び下側貫通開口６０が形成されている。説明の重複を避けるために、陽極板５６の詳細な説明は省略する。 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 for an anode, such as titanium with an indium oxide plated surface. be. More specifically, the cathode plate 32 and the anode plate 56 have plane symmetry between them with an imaginary plane extending perpendicularly to the plane of the paper in FIG. 1 as a plane of symmetry. Therefore, the anode plate 56 has a rectangular shape that extends continuously 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. To avoid duplication of explanation, detailed explanation of the anode plate 56 will be omitted.

　図示の実施形態においては、陽極枠体６と陽極板５６との間にもガスケット６２が介在されている。このガスケット６２も、陰極枠体４と陰極板３２との間に介在されているガスケット３８と実質上同一である。更に詳しくは、ガスケット３８とガスケット６２とは両者間を図１において紙面に垂直に延びる仮想面を対称面とする面対称をなす。従って、ガスケット６２には、陽極枠体６に形成されている上側開口４４と陽極板５６に形成されている上側貫通開口５８を連通する上側連通開口６４と共に陽極枠体６に形成されている下側開口４８と陽極板５６に形成されている下側貫通開口６０を連通する下側連通開口６６が形成されている。説明の重複を避けるために、ガスケット６２並びに上側連通開口６４及び下側連通開口６６の詳細については説明を省略する。 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 have plane symmetry between them with an imaginary plane extending perpendicularly to the plane of the paper in FIG. 1 as a plane of symmetry. Therefore, the gasket 62 includes an upper communication opening 64 that communicates between the upper opening 44 formed in the anode frame 6 and the upper through-hole 58 formed in the anode plate 56, as well as the lower communication opening 64 formed in the anode frame 6. A lower communication opening 66 is formed that communicates the side opening 48 and the lower through-hole 60 formed in the anode plate 56 . To avoid duplication of explanation, detailed explanations of the gasket 62, the upper communication opening 64, and the lower communication opening 66 will be omitted.

　図１を参照することによって明確に理解されるとおり、図示の実施形態においては、陰極板３２と陽極板５６との間にはカチオン交換膜６８が配設されている。それ自体は周知の形態でよいカチオン交換膜６８は矩形板形状であり、その上端縁部は陰極側上壁部材８と陽極側上壁部材１０の間に把持され、その下端縁部は陰極側下壁部材１２と陽極側下壁部材１４との間に把持され、陰極枠体４及び陽極枠体６の前面側縁部は陰極側前壁部材１６と陽極側前壁部材の間に把持され、陰極枠体４及び陽極枠体６の後面側縁部は陰極側後壁部材１８と陽極側後壁部材との間に把持されている。カチオン交換膜６８と陰極側上壁部材８及び陽極側上壁部材１０、陰極側下壁部材１２及び陽極側下壁部材１４、陰極側前壁部材１６と陽極側前壁部材、並びに陰極側後壁部材１８と陽極側後壁部材の各々との間には適宜のシール部材（図示していない）を介在させることができる。 As will be clearly understood by referring to FIG. 1, in the illustrated embodiment, a cation exchange membrane 68 is disposed between the cathode plate 32 and the anode plate 56. The cation exchange membrane 68, which itself may have a well-known form, has a rectangular plate shape, and its upper edge is held between the cathode side upper wall member 8 and the anode side upper wall member 10, and its lower edge is on the cathode side. 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. Cation exchange membrane 68, 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, and cathode side rear A suitable sealing member (not shown) can be interposed between the wall member 18 and each of the anode side rear wall members.

　上述したとおりの電解槽においては、陰極板３２とカチオン交換膜６８との間に陰極室乃至製品室７０が規定され、陽極板５６とカチオン交換膜６８との間に陽極室即ち原料室７２が規定されている。そして、当初は希釈化された水酸化第４級アンモニウム水溶液（又は純水）が製品室７０を通して循環され、更に詳しくは陰極枠体４に形成されている下側流路２６と上側流路２２との一方を通して製品室７０に流入され他方を通して製品室７０から流出される。同時に、４級アンモニウム塩水溶液が原料室７２を通して循環され、更に詳しくは陽極枠体６に形成されている下側流路５０と上側流路４６との一方を通して原料室７２に流入され他方を通して流出される。陰極板３２と陽極板５６との間には電解電圧が印加される。かくして、製品室７０を循環する水酸化第４級アンモニウム水溶液の濃度が漸次増大される。かような電解作用は当業者には周知であるので、その詳細な説明は本明細書においては省略する。而して、本発明に従って構成された電解槽の図示の実施形態においては、陰極板３２及び陽極板５６の各々は陰極枠体４及び陽極枠体６に形成されている上側開口２０及び４４よりも上方から下側開口２４及び４８よりも下方まで連続して延びる形態であり、陰極板３２及び陽極板５６の各々に上側開口２０及び４４並びに下側開口２４及び４８に整合する上側貫通開口３４及び５８並びに下側貫通開口３６及び６０が形成されている故に、陰極板３２及び陽極板５６は夫々陰極枠体４及び陽極枠体６の内面の略全体に渡って延在し、従って電解槽の大きさに対する陰極板３２及び陽極板５６の相対的通電面積が大きく、かくして向上された電解効率によって電解が遂行される。 In the electrolytic cell as described above, a cathode chamber or product chamber 70 is defined between the cathode plate 32 and the cation exchange membrane 68, and an anode chamber or raw material chamber 72 is defined between the anode plate 56 and the cation exchange membrane 68. stipulated. Initially, a diluted quaternary ammonium hydroxide aqueous solution (or pure water) is circulated through the product chamber 70, and more specifically, the lower flow path 26 and the upper flow path 22 formed in the cathode frame 4. It flows into the product chamber 70 through one of the two and flows out from the product chamber 70 through the other. At the same time, the quaternary ammonium salt aqueous solution is circulated through the raw material chamber 72, and more specifically, it 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 out through the other. be done. An electrolytic voltage is applied between the cathode plate 32 and the anode plate 56. In this way, the concentration of the quaternary ammonium hydroxide aqueous solution circulating in the product chamber 70 is gradually increased. Since such electrolysis is well known to those skilled in the art, a detailed explanation thereof will be omitted herein. Thus, in the illustrated embodiment of an electrolytic cell constructed in accordance with the present invention, the cathode plate 32 and the anode plate 56 extend through the

upper openings

20 and 44 formed in the cathode frame 4 and anode frame 6, respectively. The upper through-hole 34 extends continuously from above to below the

lower openings

24 and 48, and is aligned with the

upper openings

20 and 44 and the

lower openings

24 and 48 in the cathode plate 32 and the anode plate 56, respectively. and 58 and lower through

openings

36 and 60, 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, and therefore the electrolytic cell The relative current-carrying areas of the cathode plate 32 and the anode plate 56 are large relative to the size of the anode plate , and thus electrolysis is performed with improved electrolysis efficiency.

　本発明に従って構成された電解槽においては、陰極側流体排出路の有効流路断面積ＣＤは陰極側流体供給路の有効流路断面積ＣＳよりも大きく、同様に陽極側流体排出路の有効流路断面積ＡＤは陽極側流体供給路の有効流路断面積ＡＳよりも大きいことが重要である。語句「有効流路断面積」は流路中の最小横断面積を意味する。図示の実施形態においては、陰極側流体排出路ＣＤは、陰極板３２の形成されている６個の上側貫通開口３４と共に上側貫通開口３４に続く上側連通開口４０、上側開口２０、上側流路２２及び外側流路３１の一部によって規定されており、上側連通開口３４、上側開口２０、上側流路２２及び外側流路３１の一部の横断面積は上側貫通開口３４の横断面積と同一或いはこれよりも大きく、従って陰極側流体排出路の有効流路断面積ＣＤは６個の上側貫通開口３４の合計横断面積によって規定される。また、陰極側流体供給路の有効流路断面積ＣＳは、陰極板３２に形成されている３個の下側貫通開口３６と共に下側貫通開口３６に続く下側連通開口４２、下側開口２４、下側流路２６及び外側流路３１の一部によって規定されており、下側連通開口４２、下側開口２４、下側流路２６及び外側流路３１の一部の横断面積は下側貫通開口３６の横断面積と同一或いはこれよりも大きく、従って陰極側流体排出路の有効流路断面積ＣＤは３個の下側貫通開口３６の合計横断面積によって規定される。特に排出される流体による背圧上昇の抑制の観点から、外側流路３１の一部の横断面積は、上側貫通開口３４乃至下側貫通開口３６の横断面積よりも大きいことが好ましい。具体的には、外側流路３１の一部の横断面積は、上側貫通開口３４乃至下側貫通開口３６の横断面積の１．０倍以上が好ましく、１．５倍以上がより好ましい。上側貫通開口３４乃至下側貫通開口３６に対する外側流路３１の一部の横断面積は、有効流路断面積と流体の供給量を勘案して適宜決定される。 In the electrolytic cell constructed according to the present invention, the effective flow cross-sectional area CD of the cathode-side fluid discharge passage is larger than the effective flow cross-sectional area CS of the cathode-side fluid supply passage, and similarly, the effective flow cross-sectional area CD of the cathode-side fluid discharge passage is larger than the effective flow cross-sectional area CS of the cathode-side fluid supply passage. It is important that the passage cross-sectional area AD is larger than the effective passage cross-sectional area AS of the anode side fluid supply passage. The phrase "effective flow path cross-sectional area" means the smallest cross-sectional area in the flow path. In the illustrated embodiment, the cathode side fluid discharge path CD includes six upper through openings 34 in which the cathode plate 32 is formed, an upper communication opening 40, an upper opening 20, an upper flow path 22 following the upper through opening 34, and a part of the outer passage 31, and the cross-sectional area of the upper communication opening 34, the upper opening 20, the upper passage 22, and a part of the outer passage 31 is the same as the cross-sectional area of the upper through-opening 34, or is smaller than that. Therefore, the effective flow cross-sectional area CD of the cathode-side fluid discharge path is defined by the total cross-sectional area of the six upper through-openings 34. In addition, the effective channel cross-sectional area CS of the cathode side fluid supply channel includes three lower through openings 36 formed in the cathode plate 32, a lower communication opening 42 following the lower through opening 36, and a lower opening 24. , the lower passage 26 and a part of the outer passage 31, and the cross-sectional area of the lower communication opening 42, the lower opening 24, the lower passage 26, and a part of the outer passage 31 is defined by the lower passage 26 and a part of the outer passage 31. It is equal to or larger than the cross-sectional area of the through-opening 36, and therefore, the effective flow cross-sectional area CD of the cathode side fluid discharge path is defined by the total cross-sectional area of the three lower through-openings 36. In particular, from the viewpoint of suppressing an increase in back pressure due to discharged fluid, it is preferable that the cross-sectional area of a portion of the outer flow path 31 is larger than the cross-sectional area of the upper through-opening 34 to the lower through-opening 36. Specifically, the cross-sectional area of a portion of the outer flow path 31 is preferably 1.0 times or more, more preferably 1.5 times or more, the cross-sectional area of the upper through-opening 34 to the lower through-opening 36. The cross-sectional area of a portion of the outer flow path 31 with respect to the upper through-opening 34 to the lower through-opening 36 is appropriately determined in consideration of the effective flow path cross-sectional area and the amount of fluid supplied.

　図示の実施形態においては、上述したとおり上側貫通開口３４は幅方向（図１において紙面に垂直な方向、図２において左右方向）に等間隔をおいて６個形成されているのに対して、下側貫通開口３６は幅方向（図１において紙面に垂直な方向、図２において左右方向）に等間隔をおいて３個形成されており、６個の上側貫通開口３４の各々の横断面積と３個の下側貫通開口３６の各々の横断面積は全て同一である。従って、陰極側流体排出路の有効流路断面積ＣＤは陰極側流体供給路の有効流路断面積ＣＳの２倍である。後述する実施例からも理解される如く、陰極側流体排出路の有効流路断面積ＣＤは陰極側流体供給路の有効流路断面積ＣＳの１．１乃至３．０倍（ＣＤ＝１．１乃至３．０ＣＳ）、特に１．５乃至２．５倍（ＣＤ＝１．５乃至２．５ＣＳ）であるのが好ましい。 In the illustrated embodiment, six upper through openings 34 are formed at equal intervals in the width direction (direction perpendicular to the plane of the paper in FIG. 1, horizontal direction in FIG. 2) as described above. Three lower through openings 36 are formed at equal intervals in the width direction (direction perpendicular to the plane of the paper in FIG. 1, horizontal direction in FIG. 2), and the cross-sectional area of each of the six upper through openings 34 and The cross-sectional area of each of the three lower through-openings 36 is all the same. Therefore, the effective channel cross-sectional area CD of the cathode-side fluid discharge channel is twice the effective channel cross-sectional area CS of the cathode-side fluid supply channel. As will be understood from the examples described later, the effective flow cross-sectional area CD of the cathode-side fluid discharge path is 1.1 to 3.0 times the effective flow cross-sectional area CS of the cathode-side fluid supply path (CD=1. 1 to 3.0 CS), particularly 1.5 to 2.5 times (CD=1.5 to 2.5 CS).

　陰極板３２に形成されている上側貫通開口３４及び下側貫通開口３６の横断面積は、最大限の電界効率を達成するために必要最小限に設定することが望まれる。然るに、本発明者等は、電解槽の作動について鋭意検討及び実験を重ねた結果、陰極室乃至製品室７０においては電解作用に起因してガスが生成され、陰極側流体排出路においては陰極側流体に加えて生成されたガスも流動される。それ故に、陰極側流体排出路の有効流路断面積ＣＤを陰極側流体供給路の有効流路断面積ＣＳと同一に設定すると、陰極側流体排出路では陰極側流体供給路に比べて流速が増大されて背圧が生成され、これに起因して電解電圧が上昇され電解槽の安定した作動が阻害される傾向がある。然るに、本発明に従って構成された電解槽においては、陰極側流体排出路の有効流路断面積ＣＤは陰極側流体供給路の有効流路断面積ＣＳよりも大きく設定されている故に、後述する実施例からも明確に理解されるとおり、電解電圧の上昇が回避され電解槽の安定した作動が確保される。 It is desirable that the cross-sectional area of the upper through-opening 34 and the lower through-opening 36 formed in the cathode plate 32 be set to the minimum necessary in order to achieve maximum electric field efficiency. However, as a result of extensive studies and experiments regarding the operation of the electrolytic cell, the inventors of the present invention found that gas is generated due to electrolytic action in the cathode chamber or product chamber 70, and that gas is generated in the cathode side fluid discharge path on the cathode side. In addition to the fluid, the gas produced is also flowed. Therefore, if the effective channel cross-sectional area CD of the cathode-side fluid discharge channel is set to be the same as the effective channel cross-sectional area CS of the cathode-side fluid supply channel, the flow velocity will be lower in the cathode-side fluid discharge channel than in the cathode-side fluid supply channel. This increases backpressure, which tends to increase the electrolysis voltage and impede stable operation of the electrolyzer. However, in the electrolytic cell configured according to the present invention, the effective flow cross-sectional area CD of the cathode-side fluid discharge path is set larger than the effective flow cross-sectional area CS of the cathode-side fluid supply path. As clearly understood from the example, an increase in electrolysis voltage is avoided and stable operation of the electrolytic cell is ensured.

　図１乃至図３に図示する上述したとおりの形態においては、上側貫通開口３４の個数（６個）を下側貫通開口３６の個数（３個）よりも多くして、陰極側流体排出路の有効流路断面積ＣＤを陰極側流体供給路の有効流路断面積ＣＳよりも大きくしているが、所望ならば、上側貫通開口３４の個数と下側貫通開口３６の個数とを同一にして、上側貫通開口３４の各々の横断面積を下側貫通開口３６の各々の横断面積よりも大きく設定して、陰極側流体排出路の有効流路断面積ＣＤを陰極側流体供給路の有効流路断面積ＣＳよりも大きくすることもできる。図４に図示する変形例においては、陰極板３２の上端部には幅方向（図４において左右方向）に等間隔をおいて３個の上側貫通開口３４が形成され（従って、上側連通開口４０、上側開口２０及び上側流路２２も夫々３個形成されている）、陰極板３２の下端部には幅方向（図４において左右方向）に等間隔をおいて３個の下側貫通開口３６が形成されており、上側貫通開口３４の各々の横断面積は下側貫通開口３６の各々の横断面積の２倍に設定されている。然るに、本発明者等の経験によれば、上側貫通開口３４の各々の横断面積を下側貫通開口３６の各々の横断面積よりも大きく設定するよりも、上側貫通開口３４の個数を下側貫通開口３６の個数よりも多くする方が、排出流がより一層円滑になる傾向がある。 In the above-described embodiment shown in FIGS. 1 to 3, the number of upper through openings 34 (six) is larger than the number of lower through openings 36 (three), and the cathode side fluid discharge path is Although the effective passage cross-sectional area CD is made larger than the effective passage cross-sectional area CS of the cathode side fluid supply passage, if desired, the number of upper through openings 34 and the number of lower through openings 36 may be made the same. , the cross-sectional area of each of the upper through-openings 34 is set larger than the cross-sectional area of each of the lower through-openings 36, so that the effective flow cross-sectional area CD of the cathode-side fluid discharge path is equal to the effective flow path of the cathode-side fluid supply path. It can also be made larger than the cross-sectional area CS. In the modification shown in FIG. 4, three upper through-openings 34 are formed at equal intervals in the width direction (left-right direction in FIG. 4) at the upper end of the cathode plate 32 (therefore, the upper communication openings 40 , three upper openings 20 and three upper passages 22 are formed respectively), and three lower through openings 36 are formed at the lower end of the cathode plate 32 at equal intervals in the width direction (horizontal direction in FIG. 4). are formed, and the cross-sectional area of each of the upper through-openings 34 is set to be twice the cross-sectional area of each of the lower through-openings 36. However, according to the experience of the present inventors, rather than setting the cross-sectional area of each of the upper through-holes 34 larger than the cross-sectional area of each of the lower through-holes 36, the number of upper through-holes 34 that penetrates the lower side When the number of openings is greater than the number of openings 36, the discharge flow tends to be smoother.

　上述した実施形態及び変形例においては、陰極板３２に幅方向に等間隔をおいて複数個の上側貫通開口３４及び下側貫通開口３６を形成しているが、所望ならば陰極板３２に幅方向に細長く延在する１個の上側貫通開口及び下側貫通開口を形成し、上側貫通開口３４の横断面積を下側貫通開口３６の横断面積よりも大きくすることもできる。 In the embodiments and modifications described above, a plurality of upper through openings 34 and lower through openings 36 are formed in the cathode plate 32 at equal intervals in the width direction, but if desired, the cathode plate 32 has a plurality of widths. It is also possible to form one upper through-opening and one lower through-opening that extend elongated in the direction, and the cross-sectional area of the upper through-opening 34 to be larger than the cross-sectional area of the lower through-opening 36.

　更に、上述した実施形態及び変形例においては、陰極板３２は陰極枠体４に形成されている上側開口２０よりも上方から陰極枠体４に形成されている下側開口２４よりも下方まで連続して延在する形態であり、陰極板３２の上端部には幅方向（図１において紙面に垂直な方向、図２及び図４において左右方向）に等間隔をおいて複数個の上側貫通開口３４が形成され、陰極板３２の下端部に幅方向（図１において紙面に垂直な方向、図２及び図４において左右方向）に等間隔をおいて複数個の下側貫通開口３６が形成されているが、所望ならば、例えば陰極板３２を陰極枠体４に形成されている上側開口２０よりも下方から陰極枠体４に形成されている下側開口２４よりも上方までの間を延在する形態にして、陰極板３２には上側貫通開口３４及び下側貫通開口３６を形成することなく、陰極側流体排出路の上流端は陰極枠体４に形成された上側開口２０によって規定し、陰極側流体供給路の下流側は陰極枠体４に形成された下側開口２４によって規定することもできる。かかる場合には、陰極側流体排出路の有効流路断面積は上側開口２０の合計横断面積によって規定され、陰極側流体供給路の有効流路断面積は下側開口２４の合計横断面積によって規定される。 Furthermore, in the embodiments and modifications described above, the cathode plate 32 is continuous from above the upper opening 20 formed in the cathode frame 4 to below the lower opening 24 formed in the cathode frame 4. The upper end of the cathode plate 32 has a plurality of upper through-openings spaced at equal intervals in the width direction (direction perpendicular to the plane of the paper in FIG. 1, horizontal direction in FIGS. 2 and 4). 34 is formed, and a plurality of lower through-openings 36 are formed at the lower end of the cathode plate 32 at equal intervals in the width direction (direction perpendicular to the plane of the paper in FIG. 1, horizontal direction in FIGS. 2 and 4). However, if desired, for example, the cathode plate 32 may be extended from below the upper opening 20 formed in the cathode frame 4 to above the lower opening 24 formed in the cathode frame 4. In this case, the cathode plate 32 does not have an upper through opening 34 and a lower through opening 36, and the upstream end of the cathode fluid discharge path is defined by the upper opening 20 formed in the cathode frame 4. The downstream side of the cathode side fluid supply path can also be defined by a lower opening 24 formed in the cathode frame 4. In such a case, the effective flow cross-sectional area of the cathode side fluid discharge passage is defined by the total cross-sectional area of the upper openings 20, and the effective flow passage cross-sectional area of the cathode-side fluid supply passage is defined by the total cross-sectional area of the lower openings 24. be done.

　陰極側流体排出路の有効流路断面積ＣＤと陰極側流体供給路の有効流路断面積ＣＳとの関係について具体的に説明したが、陽極側流体排出路の有効流路断面積ＡＤと陽極側流体供給路の有効流路断面積ＡＳとの関係も全く同様であり、説明の重複をさせるために、陽極側流体排出路の有効流路断面積ＡＤと陽極側流体供給路の有効流路断面積ＡＳとの関係についての具体的な説明は省略する。 Although the relationship between the effective flow cross-sectional area CD of the cathode side fluid discharge passage and the effective flow passage cross-sectional area CS of the cathode side fluid supply passage has been specifically explained, the effective flow passage cross-sectional area AD of the anode side fluid discharge passage and the anode The relationship between the effective passage cross-sectional area AS of the side fluid supply passage is also exactly the same, and in order to avoid duplication of explanation, the effective passage cross-sectional area AD of the anode side fluid discharge passage and the effective passage cross-sectional area of the anode side fluid supply passage are A specific explanation of the relationship with the cross-sectional area AS will be omitted.

　実施例１乃至３及び比較例１
　図１乃至図３或いは図４に図示するとおりの形態の電解槽を作成し、定電流制御様式で作動させ、作動時間中のセル電圧（陽極板と陰極板との間の電圧）の平均値を検出した。実施例１乃至３においては、陰極側流体排出路の有効流路断面積ＣＤは陰極側流体供給路の有効流路断面積ＣＳよりも大きく、同様に陽極側流体排出路の有効流路断面積ＡＤは陽極側流体供給路の有効流路断面積ＡＳよりも大きかった。一方、比較例１においては、陰極側流体排出路の有効流路断面積ＣＤと陰極側流体供給路の有効流路断面積ＣＳとは同一であり、同様に陽極側流体排出路の有効流路断面積ＡＤと陽極側流体供給路の有効流路断面積ＡＳとは同一であった。セル電圧の平均値は表１に示すとおりであった。 Examples 1 to 3 and comparative example 1
An electrolytic cell having the configuration as shown in FIGS. 1 to 3 or 4 is prepared and operated in a constant current control mode, and the average value of the cell voltage (voltage between the anode plate and the cathode plate) during the operation time is was detected. In Examples 1 to 3, the effective channel cross-sectional area CD of the cathode-side fluid discharge channel is larger than the effective channel cross-sectional area CS of the cathode-side fluid supply channel, and similarly the effective channel cross-sectional area of the anode-side fluid discharge channel is AD was larger than the effective channel cross-sectional area AS of the anode side fluid supply channel. On the other hand, in Comparative Example 1, the effective channel cross-sectional area CD of the cathode-side fluid discharge channel and the effective channel cross-sectional area CS of the cathode-side fluid supply channel are the same, and similarly, the effective channel cross-sectional area CD of the cathode-side fluid discharge channel is the same. The cross-sectional area AD and the effective channel cross-sectional area AS of the anode side fluid supply channel were the same. The average value of cell voltage was as shown in Table 1.

　電解槽の構成要素の詳細及び作動状態は、次のとおりである。
　　　　　　　作動時間：　３０日間
　　　　　　　　　陰極：ニッケル板（厚さ２ｍｍ、表面寸法１ｍ×１ｍ）
　　　　　　　　　陽極：表面に酸化インジウムをメッキしたチタン板（厚
　　　　　　　　　　　さ２ｍｍ、表面寸法１ｍ×１ｍ）
　　　　カチオン交換膜：ケマーズ社（Ｃｈｅｍｏｕｒｓ　Ｃｏｍｐａｎｙ
　　　　　　　　　　　）から製品名「Ｎ３２４」として販売されている交
　　　　　　　　　　　換膜（厚さ１ｍｍ）
　　　　　　ガスケット：ＥＰＤＭ（上側連通開口及び下側連通開口の直径
　　　　　　　　　　　は対応する上側貫通開口及び下側貫通開口の直径よ
　　　　　　　　　　　り夫々２ｍｍ大きい）
　　　原料（陽極側流体）：塩化メチルアンモニウム水溶液
　　　製品（陰極側流体）：水酸化メチルアンモニウム水溶液
　　　　　　　　　電流：１０００Ａ（１０Ａ／ｄｍ^２）
　　　　　　　作動温度：７０℃
　電解槽組み立て時温度：２０℃
原料（陽極側流体）流量：２０Ｌ／ｍｉｎ
製品（陰極側流体）流量：２０Ｌ／ｍｉｎ The details and operating conditions of the electrolytic cell components are as follows.
Operating time: 30 days Cathode: Nickel plate (thickness 2mm, surface dimensions 1m x 1m)
Anode: Titanium plate with indium oxide plated on the surface (thickness 2mm, surface dimensions 1m x 1m)
Cation exchange membrane: Chemours Company
) Replacement membrane (thickness 1mm) sold under the product name “N324”
Gasket: EPDM (the diameters of the upper and lower communication openings are 2 mm larger than the corresponding diameters of the upper and lower through-holes, respectively)
Raw material (anode side fluid): Methylammonium chloride aqueous solution Product (cathode side fluid): Methylammonium hydroxide aqueous solution Current: 1000A (10A/dm ² )
Operating temperature: 70℃
Temperature when assembling electrolytic cell: 20℃
Raw material (anode side fluid) flow rate: 20L/min
Product (cathode side fluid) flow rate: 20L/min

　本発明の好適実施形態を図示している添付図面を参照して詳細に説明したが、本発明はかかる実施形態に限定されるものではなく、本発明の技術的範囲から逸脱することなく種々の変形乃至修正が可能であることは多言を要しない。例えば、図示の実施形態においては、陰極板３２と陽極板５６との間に１個のカチオン交換膜６８が配設されているが、陰極板３２と陽極板５６との間に複数個の交換膜（カチオン交換膜及びアニオン交換膜）が配設されている電解槽にも本発明を適用することができる。 Although the present invention has been described in detail with reference to the accompanying drawings illustrating preferred embodiments of the present invention, the present invention is not limited to such embodiments, and may be modified in various ways without departing from the scope of the present invention. It goes without saying that it can be modified or modified. For example, in the illustrated embodiment, one cation exchange membrane 68 is disposed between cathode plate 32 and anode plate 56, but a plurality of cation 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 provided.

　　　２：電解槽のハウジング
　　　４：陰極枠体
　　　６：陽極枠体
　　　８：陰極側上壁部材
　　１０：陽極側上壁部材
　　１２：陰極側下壁部材
　　１４：陽極側下壁部材
　　１６：陰極側前壁部材
　　１８：陰極側後壁部材
　　２０：上側開口
　　２２：上側流路
　　２４：下側開口
　　２６：下側流路
　　３１：外側流路
　　３２：陰極板
　　３４：上側貫通開口
　　３６：下側貫通開口
　　３８：ガスケット
　　４０：上側連通開口
　　４２：下側連通開口
　　４４：上側開口
　　４６：上側流路
　　４８：下側開口
　　５０：下側流路
　　５６：陽極板
　　５８：上側貫通開口
　　６０：下側貫通開口
　　６２：ガスケット
　　６４：上側連通開口
　　６６：下側連通開口
　　６８：カチオン交換膜
　　７０：製品室（陰極室）
　　７２：原料室（陽極室） 2: Electrolytic cell housing 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: Outside channel 32: Cathode plate 34: Upper through opening 36: Lower through opening 38: Gasket 40: Upper communication opening 42: Lower communication 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 room (anode room)

Claims

　内面に陰極板が固定された陰極枠体と、内面に陽極板が固定された陽極枠体と、該陰極枠体と該陽極枠体との間に配設されたイオン交換膜と、該陰極枠体と該イオン交換膜との間に規定された陰極室に陰極側流体を供給するための陰極側流体供給路と、該陰極室から陰極側流体を排出するための陰極側流体排出路と、該陽極枠体と該イオン交換膜との間に規定された陽極室に陽極側流体を供給するための陽極側流体供給路と、該陽極室から陽極側流体を排出するための陽極側流体排出路とを含む電解槽において、
　該陰極側流体排出路の有効流路断面積ＣＤは該陰極側流体供給路の有効流路断面積ＣＳよりも大きく、該陽極側流体排出路の有効流路断面積ＡＤは該陽極側流体供給路の有効流路断面積ＡＳよりも大きい、
　ことを特徴とする電解槽。 A cathode frame having a cathode plate fixed to its inner surface, an anode frame having an anode plate fixed to its inner surface, an ion exchange membrane disposed between the cathode frame and the anode frame, and the cathode. a cathode side fluid supply path for supplying a cathode side fluid to a cathode chamber defined between the frame and the ion exchange membrane; and a cathode side fluid discharge path for discharging the cathode side fluid from the cathode chamber. , an anode side fluid supply path for supplying an anode side fluid to an anode chamber defined between the anode frame and the ion exchange membrane, and an anode side fluid for discharging the anode side fluid from the anode chamber. In an electrolytic cell including a discharge path,
The effective passage cross-sectional area CD of the cathode-side fluid discharge passage is larger than the effective passage cross-sectional area CS of the cathode-side fluid supply passage, and the effective passage cross-sectional area AD of the anode-side fluid discharge passage is larger than the effective passage cross-sectional area CS of the cathode-side fluid supply passage. larger than the effective flow cross-sectional area AS of the channel,
An electrolytic cell characterized by:
　該有効流路断面積ＣＤは該有効流路断面積ＣＳの１．１乃至３．０倍（ＣＤ＝１．１乃至３．０ＣＳ）であり、該有効流路断面積ＡＤは該有効流路断面積ＡＳの１．１乃至３．０倍（ＡＤ＝１．１乃至３．０ＡＳ）である、請求項１記載の電解槽。 The effective channel cross-sectional area CD is 1.1 to 3.0 times the effective channel cross-sectional area CS (CD=1.1 to 3.0 CS), and the effective channel cross-sectional area AD is 1.1 to 3.0 times the effective channel cross-sectional area CS. The electrolytic cell according to claim 1, having a cross-sectional area of 1.1 to 3.0 times AS (AD=1.1 to 3.0 AS).
　該有効流路断面積ＣＤは該有効流路断面積ＣＳの１．５乃至２．５倍（ＣＤ＝１．５乃至２．５ＣＳ）であり、該有効流路断面積ＡＤは該有効流路断面積ＡＳの１．５乃至２．５倍（ＡＤ＝１．５乃至２．５ＡＳ）である、請求項２記載の電解槽。 The effective channel cross-sectional area CD is 1.5 to 2.5 times the effective channel cross-sectional area CS (CD=1.5 to 2.5 CS), and the effective channel cross-sectional area AD is 1.5 to 2.5 times the effective channel cross-sectional area CS. The electrolytic cell according to claim 2, wherein the cross-sectional area is 1.5 to 2.5 times AS (AD=1.5 to 2.5 AS).
　該陰極枠体には、該内面の上端部に位置する上側開口から延びる少なくとも１個の上側流路及び該内面の下端部に位置する下側開口から延びる少なくとも１個の下側流路が配設されており、
　該陽極枠体には、該内面の上端部に位置する上側開口から延びる少なくとも１個の上側流路及び該内面の下端部に位置する下側開口から延びる少なくとも１個の下側流路が配設されており、
　該陰極板は該陰極枠体の該上側開口よりも上方から該陰極枠体の該下側開口よりも下方まで連続して延在し、
　該陰極板の上端部には該陰極枠体の該上側開口に整合する少なくとも１個の上側貫通開口が形成されており、該陰極板の下端部には該陰極枠体の該下側開口に整合する少なくとも１個の下側貫通開口が形成されており、
　該陽極板は該陽極枠体の該上側開口よりも上方から該陽極枠体の該下側開口よりも下方まで連続して延在し、
　該陽極板の上端部には該陽極枠体の該上側開口に整合する少なくとも１個の上側貫通開口が形成されており、該陽極板の下端部には該陽極枠体の該下側開口に整合する少なくとも１個の下側貫通開口が形成されており、
　該陰極板の該上側貫通開口及び該陰極枠体の該上側流路が該陰極側流体排出路と該陰極側流体供給路との一方を構成し、該陰極板の該下側貫通開口及び該陰極枠体の該下側流路が該陰極側流体排出路と該陰極側流体供給路との他方を構成し、
　該陽極板の該上側貫通開口及び該陽極枠体の該上側流路が該陽極側流体排出路と該陽極側流体供給路との一方を構成し、該陽極板の該下側貫通開口及び該陽極枠体の該下側流路が該陽極側流体排出路と該陽極側流体供給路との他方を構成する、
　請求項１から３までのいずれかに記載の電解槽。 The cathode frame is provided with at least one upper channel extending from an upper opening located at an upper end of the inner surface and at least one lower channel extending from a lower opening located at a lower end of the inner surface. has been established,
The anode frame has at least one upper channel extending from an upper opening located at an upper end of the inner surface and at least one lower channel extending from a lower opening located at a lower end of the inner surface. has been established,
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 at least one upper through opening aligned with the upper opening of the cathode frame. at least one lower through opening is formed in alignment;
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 at least one upper through opening aligned with the upper opening of the anode frame. at least one lower through opening is formed in alignment;
The upper through-opening of the cathode plate and the upper passage of the cathode frame constitute one of the cathode-side fluid discharge passage and the cathode-side fluid supply passage; The lower flow path of the cathode frame constitutes the other of the cathode fluid discharge path and the cathode fluid supply path,
The upper through-opening of the anode plate and the upper passage of the anode frame constitute one of the anode-side fluid discharge passage and the anode-side fluid supply passage; the lower flow path of the anode frame constitutes the other of the anode side fluid discharge path and the anode side fluid supply path;
An electrolytic cell according to any one of claims 1 to 3.
　該陰極枠体には、該内面の上端部に幅方向に間隔をおいて配置された複数個の上側開口から延びる複数個の上側流路及び該内面の下端部に幅方向に間隔をおいて配置された複数個の下側開口から延びる複数個の下側流路が配設されており、
　該陽極枠体には、該内面の上端部に幅方向に間隔をおいて配置された複数個の上側開口から延びる複数個の上側流路及び該内面の下端部に幅方向に間隔をおいて配置された複数個の下側開口から延びる複数個の下側流路が配設されており、
　該陰極板の上端部には該陰極枠体の該複数個の上側開口の各々に夫々整合する複数個の上側貫通開口が形成されており、該陰極板の下端部には該陰極枠体の該複数個の下側開口の各々に夫々整合する複数個の下側貫通開口が形成されており、
　該陽極板の上端部には該陽極枠体の該複数個の上側開口の各々に夫々整合する複数個の上側貫通開口が形成されており、該陽極板の下端部には該陽極枠体の該複数個の下側開口の各々に夫々整合する複数個の下側貫通開口が形成されており、
　該陰極側流体排出路を構成する該陰極板の該上側貫通開口及び該陰極枠体の該上側流路又は該陰極板の該下側貫通開口及び該陰極枠体の該下側流路の数は、該陰極側流体供給路を構成する該陰極板の該下側貫通開口及び該陰極枠体の該下側流路又は該陰極板の該上側貫通開口及び該陰極枠体の該上側流路の数よりも多く、
　該陽極側流体排出路を構成する該陽極板の該上側貫通開口及び該陽極枠体の該上側流路又は該陽極板の該下側貫通開口及び該陽極枠体の該下側流路の数は、該陽極側流体供給路を構成する該陽極板の該下側貫通開口及び該陽極枠体の該下側流路又は該陽極板の該上側貫通開口及び該陽極枠体の該上側流路の数よりも多い、
　請求項４記載の電解槽。 The cathode frame includes a plurality of upper channels extending from a plurality of upper openings arranged at intervals in the width direction at an upper end of the inner surface, and a plurality of upper channels extending at intervals in the width direction at a lower end of the inner surface. A plurality of lower flow passages extending from the plurality of lower openings are arranged,
The anode frame includes a plurality of upper channels extending from a plurality of upper openings arranged at intervals in the width direction at an upper end of the inner surface, and a plurality of upper channels extending at intervals in the width direction at a lower end of the inner surface. A plurality of lower flow passages extending from the plurality of lower openings are arranged,
A plurality of upper through-openings are formed at the upper end of the cathode plate, each of which aligns with each of the upper openings of the cathode frame, and a lower end of the cathode plate is formed with a plurality of upper through openings that are aligned with each of the plurality of upper openings of the cathode frame. A plurality of lower through openings are formed that respectively align with each of the plurality of lower openings,
A plurality of upper through openings are formed at the upper end of the anode plate, each of which aligns with each of the upper openings of the anode frame, and a lower end of the anode plate is formed with a plurality of upper through openings that are aligned with each of the upper openings of the anode frame. A plurality of lower through openings are formed that respectively align with each of the plurality of lower openings,
The number of the upper through-opening of the cathode plate and the upper flow path of the cathode frame or the lower through-opening of the cathode plate and the lower flow path of the cathode frame that constitute the cathode side fluid discharge path. is the lower through-opening of the cathode plate and the lower channel of the cathode frame, or the upper through-opening of the cathode plate and the upper channel of the cathode frame, which constitute the cathode-side fluid supply channel; more than the number of
The number of the upper through-opening of the anode plate and the upper flow path of the anode frame or the lower through-opening of the anode plate and the lower flow path of the anode frame that constitute the anode side fluid discharge path. is the lower through-opening of the anode plate and the lower flow path of the anode frame, or the upper through-opening of the anode plate and the upper flow path of the anode frame, which constitute the anode-side fluid supply path; more than the number of
The electrolytic cell according to claim 4.
　該陰極枠体の該上側開口及び該下側開口並びに該陰極板の該上側貫通開口及び該下側貫通開口は円形断面形状を有し、
　該陽極枠体の該上側開口及び該下側開口並びに該陽極板の該上側貫通開口及び該下側貫通開口は円形断面形状を有する、
　請求項５記載の電解槽。 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 5.
　該陰極板及び該陽極板は矩形板から構成されている、請求項４記載の電解槽。 The electrolytic cell according to claim 4, wherein the cathode plate and the anode plate are composed of rectangular plates.
　該陰極板と該陽極板との間には少なくとも１個の陽イオン交換膜が配置されている、請求項１から３までのいずれかに記載の電解槽を使用して、第４級アンモニウム塩水溶液を原料として水酸化第４級アンモニウム水溶液を製造する方法。 The electrolytic cell according to any one of claims 1 to 3, wherein at least one cation exchange membrane is arranged between the cathode plate and the anode plate, is used to produce a quaternary ammonium salt. A method for producing an aqueous quaternary ammonium hydroxide solution using an aqueous solution as a raw material.