JPS5924194B2 - electrode chamber - Google Patents

Description

【発明の詳細な説明】 本発明は隔膜式の電解槽、特に電解に伴ない気泡を発生
する物質を電解するに適した電解槽の電極室に係る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diaphragm type electrolytic cell, and particularly to an electrode chamber of an electrolytic cell suitable for electrolyzing substances that generate bubbles during electrolysis.

本発明の目的は、電解時に電極で発生する気泡の影響を
少なくし、電解槽の有効高さを大きくし得る電極室構造
を提供する。An object of the present invention is to provide an electrode chamber structure that can reduce the influence of bubbles generated at the electrode during electrolysis and increase the effective height of the electrolytic cell.

従来、隔膜式の電解槽、例えばアルカリ金属ハロゲン化
物水溶液の電解に用いる電解槽にあつては、多孔性電極
が使用される場合が多く、該電極の背後は電極室として
、電解液が満されている。Conventionally, in diaphragm-type electrolytic cells, such as electrolytic cells used for electrolyzing aqueous alkali metal halide solutions, porous electrodes are often used, and the area behind the electrodes serves as an electrode chamber filled with electrolyte. ing.

この場合、多孔性電極は、通常棒状金属を多数平行に並
べた格子状、金網状エキスパンドメタル、或いは讃孔板
等である。また多孔性電極と対向する面（即ち背面）は
、電極室を構成するための背面壁であり、場合によつて
背面壁と多孔性電極との間に電極室液のダウン・カマー
（下降流域）を形成するための仕切板が電極に直接対向
する背面板となつていることもある。更に電極端部周辺
は電極室枠によつて囲まれ、電極と背面壁と電極室枠と
により電極室が構成される。ここで電極が陽極である場
合は陽極室、また陰極である場合は陰極室とも称するが
、これらを総称して本明細書においては電極室と称する
。上記のような隔膜式電解槽にあつては、陰、陽画電極
室の間に隔膜を配し、各電極室には、液及び（又は）ガ
スの排出口及び（又は）供給口が設けられている。In this case, the porous electrode is usually in the form of a lattice in which a large number of rod-shaped metals are arranged in parallel, expanded metal in the form of a wire mesh, or a hole plate. In addition, the surface facing the porous electrode (i.e., the back surface) is a back wall for forming an electrode chamber, and in some cases, there may be a downcomer (downward region) of the electrode chamber liquid between the back wall and the porous electrode. ) is sometimes used as a back plate directly facing the electrode. Furthermore, the periphery of the electrode end portion is surrounded by an electrode chamber frame, and the electrode chamber is constituted by the electrode, the back wall, and the electrode chamber frame. Here, when the electrode is an anode, it is also referred to as an anode chamber, and when it is a cathode, it is also referred to as a cathode chamber, but these are collectively referred to as the electrode chamber in this specification. In the case of a diaphragm type electrolytic cell as described above, a diaphragm is arranged between the negative and positive electrode chambers, and each electrode chamber is provided with a liquid and/or gas discharge port and/or supply port. ing.

例えば塩化ナトリウム水溶液の電解について説明すると
、陽極室に塩化ナトリウム水溶液を供給すれば隔膜を通
して陰極室にナトリウムイオン、水及び場合によつて塩
素イオンが移行する。陽極では塩素イオンが酸化され、
塩素ガスの気泡となつて陽極室液中を上昇し、ガス排出
口より抜き出される。また陰極では水素イオンが還元さ
れ、水素ガスが気泡として、陰極室液中を上昇し、ガス
排出口より抜き出される。更に陰極室液は苛性ソーダと
して取り出される。この場合隔膜として陽イオン交換膜
を用いると、実質的に塩素イオンは陰極室に移行せず、
水もナトリウムイオンの水和水を除いて実質的に陰極室
には移行しないため、高純度及び高濃度の苛件ソーダが
得られるという利点がある。更にイオン交換膜は一般に
強度が大きく薄いため、陰、陽両電極間の間隔を小さく
できること、また表面が滑らかであるため気泡を停滞せ
しめない等の利点がある。以下に述べる本発明にあつて
も、隔膜と電極前面（隔膜に対向する面）との間隔は狭
゜く、しかも使用時において常に所定の間隔、例えば１
乃至５ｍｍに保つことが好ましいので、隔膜としてイオ
ン交換膜を用いることが推奨される。本発明は、上記の
如き電解槽において．電解時に電極で発生する気泡の影
響を低下させることができる特殊な電極室を提供する。For example, to explain the electrolysis of an aqueous sodium chloride solution, when an aqueous sodium chloride solution is supplied to an anode chamber, sodium ions, water, and in some cases chlorine ions are transferred to the cathode chamber through a diaphragm. At the anode, chlorine ions are oxidized,
Chlorine gas bubbles rise in the anode chamber liquid and are extracted from the gas outlet. Further, hydrogen ions are reduced at the cathode, and hydrogen gas rises in the cathode chamber liquid as bubbles and is extracted from the gas outlet. Furthermore, the cathode chamber solution is taken out as caustic soda. In this case, if a cation exchange membrane is used as the diaphragm, chlorine ions will not substantially migrate to the cathode chamber.
Since water does not substantially migrate to the cathode chamber except for hydration water of sodium ions, there is an advantage that caustic soda of high purity and high concentration can be obtained. Further, since ion exchange membranes are generally strong and thin, they have the advantage that the distance between the negative and positive electrodes can be reduced, and their smooth surfaces prevent air bubbles from becoming stagnant. Even in the present invention described below, the distance between the diaphragm and the front surface of the electrode (the surface facing the diaphragm) is narrow, and moreover, during use, it is always kept at a predetermined distance, e.g.
Since it is preferable to keep the thickness between 5 mm and 5 mm, it is recommended to use an ion exchange membrane as the diaphragm. The present invention provides an electrolytic cell as described above. To provide a special electrode chamber capable of reducing the influence of bubbles generated at the electrode during electrolysis.

即ち、本発明の電極室は、多孔註電極とこれに対向する
背面壁と、これらの周辺に存在する電極室枠とで囲んだ
函状体の内部に、多孔性電極に向つて昇り勾配の案内板
を設けることが最大の特徴である。That is, the electrode chamber of the present invention has a box-shaped body surrounded by a porous electrode, a back wall facing thereto, and an electrode chamber frame existing around these, and has an upward slope toward the porous electrode. The biggest feature is that it has a guide board.

上記案内板を電極室内に設けることによつて．電極多孔
面に滞留している気泡を洗い流し気泡密度を低下させる
ことができる。By installing the above guide plate inside the electrode chamber. It is possible to wash away the air bubbles staying on the porous electrode surface and reduce the air bubble density.

本発明の案内板は．電極室内に多孔件電極に向つて昇り
勾配を有するように存在させればよく、その固定方法は
特に限定されないが．背面壁に固定するか、或いは電極
室枠通常その両側壁部及び（又（１）電導リブに固定す
るのが好ましい。The information board of the present invention is. The porous electrode may be placed in the electrode chamber so as to have an upward slope toward the electrode, and the method of fixing the porous electrode is not particularly limited. It is preferable to fix it to the back wall, or to the electrode chamber frame, usually its side walls, and (1) the conductive ribs.

固定に際しては、案内板の昇り勾配が３０度乃至６０度
の仰角となるように設けるのが好ましい。また６案内板
は電極室の幅方向にほぼ全巾に亘つて設けるのが好まし
く、しかも高さ方向に５ＣＴ！Ｌ乃至３０？間隙で複数
枚設けるのか好ましい。更に多孔性電極と背面壁との間
隔もあまり大きいことは好ましくなく２０〜５０鼎程度
がよい。本発明に使用される案内板は平滑な板状であつ
ても或いは凹凸を有する板でちつてもよい。また案内板
の上と下で圧力バランスを保つために案内板に開口部を
持たせてもよい。開口部の形状は特に限定されないが開
口部の位置は背面壁に近い位置程好ましい。開口部が案
内板の全面積に占める割合は開口部の形状等によつて変
わるか．一般には開口率が約３０％以下か好ましく．開
口率が３０％を越えると．案内板の効果を減することが
ある。案内板の材質は電極室液に安定で、ある程度の強
度を有しておれば特に限定されず，種々のものが用いら
れる。When fixing, it is preferable to provide the guide plate so that the upward slope thereof becomes an elevation angle of 30 degrees to 60 degrees. Moreover, it is preferable to provide 6 guide plates over almost the entire width in the width direction of the electrode chamber, and 5CT in the height direction! L to 30? It is preferable to provide a plurality of sheets at intervals. Further, it is not preferable that the distance between the porous electrode and the back wall be too large, and it is preferably about 20 to 50 degrees. The guide plate used in the present invention may be a smooth plate or may be a plate having unevenness. Further, the guide plate may have an opening in order to maintain pressure balance above and below the guide plate. Although the shape of the opening is not particularly limited, the position of the opening is preferably closer to the back wall. Does the ratio of the opening to the total area of the guide plate change depending on the shape of the opening, etc.? Generally, it is preferable that the aperture ratio is approximately 30% or less. When the aperture ratio exceeds 30%. This may reduce the effectiveness of information boards. The material of the guide plate is not particularly limited as long as it is stable to the electrode chamber liquid and has a certain degree of strength, and various materials can be used.

例えば陽極室に案内板を設ける場合はチタン，ポリプロ
ピレン、ポリエチレン、ポリスチレン等が．また陰極室
に設ける場合は鉄、ニツケル、ポリプロピレン．ポリエ
チレン．ポリスチレン等の材質が好ましく使用される。
以上のような案内板を有する電極室を用いる時、多孔性
電極の有効高さが１００？以上となつても６通常の堅型
電解槽における程に気泡による弊害が生じない。For example, when installing a guide plate in the anode chamber, use titanium, polypropylene, polyethylene, polystyrene, etc. If installed in the cathode chamber, use iron, nickel, or polypropylene. polyethylene. Materials such as polystyrene are preferably used.
When using an electrode chamber with a guide plate as described above, the effective height of the porous electrode is 100? Even with the above, the problem caused by air bubbles does not occur as much as in the case of a normal vertical electrolytic cell.

従つて．電解槽を大型化することが可能となり経済的で
ある。本発明を更に図面によつて説明する，第１図は本
発明の電極室を有する電解槽の概念図である。Accordingly. It is possible to increase the size of the electrolytic cell, which is economical. The present invention will be further explained with reference to the drawings. FIG. 1 is a conceptual diagram of an electrolytic cell having an electrode chamber according to the present invention.

図中，１が陽極．２が陰極、３かイオン交換膜等の隔膜
．４が陽極室背面壁．５が陰極室背面壁．６が陽極室枠
、７力ｊ陰極室枠である。陽極１と背面壁４と陽極室枠
６とによつて陽極室を構成し．陰極２と背面壁５と陰極
室枠７とによつて陰極室を構成する。また８は陽極を支
え．これに電気を供給するための電導リブであり．９は
，同様に陰極側の電導リブである。また１０はパツキン
グである。この電解槽を用いて，例えば塩化ナトリウム
水溶液を電解する場合は、液供給口２０より塩水を供給
し，液及びガス抜き出し口２１より排塩水及び塩素を取
り出す。一方液供給口２２より場合によつて．水又は稀
アルカリを供給し、生成苛注ソーダ濃度を調整して抜出
し口２３より苛性ソーダ及び水素を取り出す。また必要
により電極室液を循環することもできる。更に供給口、
抜出口（ま．必要に応じて適当数設けることができる。
本発明の特徴の一つは、電極室内に．多孔性電極２に向
つて昇り勾配の案内板１１が付設されている点にちる。
このように案内板を付設することによつて、循環液又は
濃度調整用として下部に供給される液及び（又は）隔膜
を透過した液は．電極で発生した気泡を包含し上昇する
が．案内板の作用により電極前面に向けて流れの方向を
かえられ、しかも案内板先端部近辺で流速が大となり、
液が矢印で示した如く電極多孔面を洗うように流れる。
このため電極表面に滞留している気泡が洗い流されると
共に．単位時間当り多量の液か通過することになり，気
泡密度を低下せしめる効果と相俟つて気泡による悪影響
を著じるしく減する。第２図は第１図と直角方向の断面
図（陰極室部分のみ）であり、案内板１１の位置を容易
に理解させるための説明図である。第２図及び以下の図
面においては、第１図と同一の部分について同一の符号
が用いられている。第２図は、案内板１１力ｊ電極室の
ほぼ全巾に亘つて設けられていることが示されている。
第２図において案内板の固定方法の例を示すと、矢印イ
の如く背面壁５に固定する方法，矢印口の如く電極室枠
７の側壁に固定する方法，更に本図の如く電導リブ９が
縦方向に設けられている場合等には矢印ハの如く電導リ
ブや補強リブに付設することもできる。In the figure, 1 is the anode. 2 is a cathode, 3 is a diaphragm such as an ion exchange membrane. 4 is the back wall of the anode chamber. 5 is the back wall of the cathode chamber. 6 is the anode chamber frame, and 7 is the cathode chamber frame. An anode chamber is constituted by an anode 1, a back wall 4, and an anode chamber frame 6. The cathode 2, the back wall 5, and the cathode chamber frame 7 constitute a cathode chamber. Also, 8 supports the anode. These are conductive ribs that supply electricity to this. Similarly, 9 is a conductive rib on the cathode side. Also, 10 is punching. When electrolyzing, for example, a sodium chloride aqueous solution using this electrolytic cell, salt water is supplied from the liquid supply port 20, and waste salt water and chlorine are taken out from the liquid and gas extraction port 21. On the other hand, from the liquid supply port 22 depending on the case. Water or dilute alkali is supplied, the concentration of caustic soda produced is adjusted, and caustic soda and hydrogen are taken out from the extraction port 23. Further, the electrode chamber liquid can be circulated if necessary. Furthermore, the supply port,
Extraction ports (appropriate number can be provided as needed.
One of the features of the present invention is that the electrode chamber is The reason for this is that a guide plate 11 having an upward slope toward the porous electrode 2 is attached.
By installing the guide plate in this way, the circulating fluid or the fluid supplied to the lower part for concentration adjustment and/or the fluid that permeates through the diaphragm can be controlled. It rises, encompassing the air bubbles generated at the electrode. The action of the guide plate changes the direction of the flow toward the front of the electrode, and the flow velocity increases near the tip of the guide plate.
The liquid flows as if washing the porous surface of the electrode as shown by the arrow.
As a result, air bubbles remaining on the electrode surface are washed away. A large amount of liquid passes through the passage per unit time, and together with the effect of lowering the bubble density, the negative effects of bubbles are significantly reduced. FIG. 2 is a cross-sectional view (only the cathode chamber portion) taken in a direction perpendicular to FIG. 1, and is an explanatory diagram for easily understanding the position of the guide plate 11. In FIG. 2 and the following drawings, the same reference numerals are used for the same parts as in FIG. 1. FIG. 2 shows that the guide plate 11 is provided over almost the entire width of the electrode chamber.
Examples of methods of fixing the guide plate in FIG. 2 include a method of fixing it to the back wall 5 as shown by arrow A, a method of fixing it to the side wall of the electrode chamber frame 7 as shown by the arrow opening, and a method of fixing it to the side wall of the electrode chamber frame 7 as shown in this figure. When the ribs are provided in the vertical direction, they can be attached to conductive ribs or reinforcing ribs as shown by arrow C.

第３図は本発明の別の態様を示す概念図であつて，陰極
室液のダウンカマ一を形成する如く仕切板１２を背面壁
５との間に設けた例である。FIG. 3 is a conceptual diagram showing another embodiment of the present invention, and is an example in which a partition plate 12 is provided between the partition plate 12 and the rear wall 5 so as to form a downcomer for the cathode chamber liquid.

仕切板１２は電極室の全高に及ばず、上部及び下部に夫
々適当な間隙を有している。このため．電極室液は矢印
の如く電極２近傍で上昇し、ダウンカマ一によつて下降
し．下部で電極側に誘導されるように電極室内で循環す
る。このような態様も本発明の好ましい一例である。以
上第１図乃至第３図においては６主として陰極室内に案
内板を付設した例で示したか、勿論，気泡を発生する電
解であれば陽極室に対しても、また陰極室及び陽極室の
両電極室に対しても付設し得るものである。The partition plate 12 does not span the entire height of the electrode chamber, and has appropriate gaps at its upper and lower parts. For this reason. The electrode chamber liquid rises near the electrode 2 as shown by the arrow, and descends by the downcomer 1. It circulates within the electrode chamber so that it is guided toward the electrode side at the bottom. Such an embodiment is also a preferred example of the present invention. In the above Figures 1 to 3, we have mainly shown an example in which a guide plate is attached to the cathode chamber, but of course, in the case of electrolysis that generates bubbles, it may also be used for the anode chamber or both the cathode chamber and the anode chamber. It can also be attached to the electrode chamber.

第４図は．本発明の電極室をフィルタープレス型双極電
極に適用した例を示す概念図である。Figure 4 is. FIG. 2 is a conceptual diagram showing an example in which the electrode chamber of the present invention is applied to a filter press type bipolar electrode.

本例では．陰極室枠７と陽極室枠６とか一体となつてお
り，また背面壁４及び５は同一の隔壁（但し第４図では
、陽極室側部材を４６陰極室側部材を５で表している）
よりなつている。通常アルカリ金属塩水溶液の電解槽に
ちつては、陽極室側部材はチタン又はゴムライニング等
でちり，陰極室側部材は軟鋼等が用いられる力Ｓ、これ
らの部材に限定されない。更に第４図において、１３は
電導リブを支える支持部材であり，１４において、隔壁
内を貫通する手段で陽極と陰極とを電気的に接続してい
る。この接続手段として、クラツド板を用いることによ
り優れた効果を期待し得る。実施例 １ 第１図に示す如き電解槽を用いる。In this example. The cathode chamber frame 7 and the anode chamber frame 6 are integrated, and the back walls 4 and 5 are the same partition wall (however, in FIG. 4, the anode chamber side member is represented by 46, and the cathode chamber side member is represented by 5).
It's getting more familiar. Usually, in an electrolytic cell for an aqueous alkali metal salt solution, the anode chamber side member is made of dust such as titanium or rubber lining, and the cathode chamber side member is made of mild steel, but is not limited to these members. Further, in FIG. 4, 13 is a support member that supports the conductive ribs, and 14 electrically connects the anode and cathode by means of penetrating the inside of the partition wall. Excellent effects can be expected by using a clad plate as this connection means. Example 1 An electrolytic cell as shown in FIG. 1 is used.

隔膜としてパーフロロスルホン酸系の陽イオン交換膜（
デユポン社製、商品名ゞナフイオン″）を配し、電極は
共にメツシユ板とし陽極は酸化ルテニウムコーテイング
チタン．陰極は軟鋼製のものを用いた。電極の有効面積
は２４ｄ〔１２０Ｃ７ｒＬ（高さ）Ｘ２Ｏ？（巾）〕で
ある。案内板は０，１ｍｍ程度の厚みを有する鉄板で作
成し．仰角４５度でその先端と陰極との間隙が約１ｍｍ
となるよう４枚等間隔に設けた。極間距離約３ｍ』陰極
室厚み４０ｍｍとし塩化ナトリウム水溶液の電解を行な
つた。電解条件は電流密度３０Ａ／Ｄｍ２、８０℃であ
つた。また、陰極室には水を供給し．生成苛件ソーダ濃
度が６Ｎとなるよう調整した。更に陰極室液（ま５１／
分の速度で循環した。この結果．極間電圧は３．６８ボ
ルトであつた。尚．上記案内板を設けない場舎について
同様に電解したところ極間電圧は３．８２ボルトであつ
た。Perfluorosulfonic acid-based cation exchange membrane (
Both electrodes were mesh plates, and the anode was made of ruthenium oxide coated titanium. The cathode was made of mild steel. The effective area of the electrode was 24 d [120C7rL (height) x2O ? (width)].The guide plate is made of a steel plate with a thickness of about 0.1 mm.At an elevation angle of 45 degrees, the gap between its tip and the cathode is about 1 mm.
Four sheets were placed at equal intervals so that Electrolysis of a sodium chloride aqueous solution was carried out using a cathode chamber with a distance of about 3 m and a cathode chamber thickness of 40 mm. The electrolytic conditions were a current density of 30 A/Dm2 and a temperature of 80°C. Also, water is supplied to the cathode chamber. The concentration of caustic soda produced was adjusted to 6N. Furthermore, the cathode chamber liquid (Ma51/
It circulated at a speed of 1 minute. As a result. The interelectrode voltage was 3.68 volts. still. When electrolysis was carried out in the same manner in a building without the above-mentioned guide plate, the inter-electrode voltage was 3.82 volts.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図及び第３図は本発明の電極室を用いた電解槽の概
念図．第２図は第１図と直角方向の断面図、第４図は本
発明の電極室を双極電極に適用した例を示す概念図であ
る。 図中、１・・・・・・陽極、２・・・・・陰極、３・・
・・・・隔膜、４・・・・・・陽極室背面壁．５・・・
・・・陰極室背面壁６６・・・・・・陽極室枠．７・・
・・・・陰極室枠、８，９・・・・・・電導リブ． １
０・・・・・・パッキング−１１・・・・・・案内板．
１２・・・・・・仕切板． １３・・・・・・支持部材
、２０・・・・・・液供給口、２１，２３・・・・・・
液及びガス抜き出し口、２２・・・・・・液供給口、を
夫々表す。Figures 1 and 3 are conceptual diagrams of an electrolytic cell using the electrode chamber of the present invention. FIG. 2 is a sectional view taken in a direction perpendicular to FIG. 1, and FIG. 4 is a conceptual diagram showing an example in which the electrode chamber of the present invention is applied to a bipolar electrode. In the figure, 1... anode, 2... cathode, 3...
...Diaphragm, 4...Anode chamber back wall. 5...
... Cathode chamber rear wall 66 ... Anode chamber frame. 7...
... Cathode chamber frame, 8, 9 ... Conductive ribs. 1
0...Packing-11...Information board.
12... Partition plate. 13... Support member, 20... Liquid supply port, 21, 23...
Represents a liquid and gas outlet port, 22...liquid supply port, respectively.

Claims (1)

【特許請求の範囲】 １ 多孔性電極とこれに対向する背面壁と、これらの周
辺に存在する電極室枠とで囲んだ歯状体の内部に、多孔
性電極に向つて昇り勾配の案内板を有する電極室。 ２ 案内板が背面壁に固定されている特許請求の範囲第
１項記載の電極室。 ３ 案内板が電導リブ及び（又は）電極室枠に固定され
ている特許請求の範囲第１項記載の電極室。 ４ 案内板が５ｃｍ乃至３０ｃｍ間隔で複数枚設けられ
ている特許請求の範囲第１項記載の電極室。 ５ 多孔性電極の有効高さが１００ｃｍ以上である特許
請求の範囲第１項記載の電極室。 ６ 多孔性電極と背面壁との間隔が２０ｍｍ乃至５０ｍ
ｍである特許請求の範囲第１項記載の電極室。 ７ 案内板に開孔部を有する特許請求の範囲第１項記載
の電極室。 ８ 案内板の昇り勾配が３０度乃至６０度の仰角を有す
る特許請求の範囲第１項記載の電極室。[Scope of Claims] 1. A guide plate that slopes upward toward the porous electrode inside a tooth-shaped body surrounded by the porous electrode, the back wall facing the porous electrode, and the electrode chamber frame existing around these. an electrode chamber with 2. The electrode chamber according to claim 1, wherein the guide plate is fixed to the back wall. 3. The electrode chamber according to claim 1, wherein the guide plate is fixed to the conductive rib and/or the electrode chamber frame. 4. The electrode chamber according to claim 1, wherein a plurality of guide plates are provided at intervals of 5 cm to 30 cm. 5. The electrode chamber according to claim 1, wherein the porous electrode has an effective height of 100 cm or more. 6 The distance between the porous electrode and the back wall is 20 mm to 50 m.
The electrode chamber according to claim 1, which is m. 7. The electrode chamber according to claim 1, which has an opening in the guide plate. 8. The electrode chamber according to claim 1, wherein the ascending slope of the guide plate has an elevation angle of 30 degrees to 60 degrees.