JPH02115387A - Electrolyzing method - Google Patents
Electrolyzing methodInfo
- Publication number
- JPH02115387A JPH02115387A JP63266017A JP26601788A JPH02115387A JP H02115387 A JPH02115387 A JP H02115387A JP 63266017 A JP63266017 A JP 63266017A JP 26601788 A JP26601788 A JP 26601788A JP H02115387 A JPH02115387 A JP H02115387A
- Authority
- JP
- Japan
- Prior art keywords
- chamber
- cation exchange
- cathode
- anode
- exchange membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title description 4
- 238000005341 cation exchange Methods 0.000 claims abstract description 56
- 239000012528 membrane Substances 0.000 claims abstract description 53
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 23
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 23
- 150000005621 tetraalkylammonium salts Chemical class 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 abstract description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003011 anion exchange membrane Substances 0.000 abstract description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 8
- -1 caustic soda Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960003067 cystine Drugs 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- WJZPIORVERXPPR-UHFFFAOYSA-L tetramethylazanium;carbonate Chemical compound [O-]C([O-])=O.C[N+](C)(C)C.C[N+](C)(C)C WJZPIORVERXPPR-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、安定して長期に連続運転が容易な電解方法に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrolysis method that is stable and easy to operate continuously over a long period of time.
陽イオン交換膜を用いた電解槽による電解方法は、有機
、無機を問わず種々の化合物を製造するのに広く使用さ
れている。一般に製造コストの低減がより重要なｎ題と
なる、例えばカセイソーダなどの化合物を工業的に製造
する方法では、陽極と陰極との間に１枚の陽イオン交換
膜を配した電解槽が用いられる。Electrolysis methods using electrolytic cells using cation exchange membranes are widely used to produce various compounds, both organic and inorganic. In general, in the industrial production of compounds such as caustic soda, where reducing production costs is a more important issue, an electrolytic cell with a single cation exchange membrane placed between an anode and a cathode is used. .
これに対して、特に高純度であることが要求されている
化合物、例えば水酸化テトラアルキルアンモニウムなど
を工業的に製造する方法では、陰極室に生成する製品に
不純物を含まないように、陽極と陰極の間に２枚以上の
陽イオン交換膜を配した電解槽を使用する態様が多い。On the other hand, in industrial methods for producing compounds that require particularly high purity, such as tetraalkylammonium hydroxide, the anode and In many cases, an electrolytic cell having two or more cation exchange membranes arranged between cathodes is used.
問に２枚以上の陽イオン交換膜を配した電解槽による電
解方法では、長期に安定して連続運転することが容易で
ないという間蝕点があった。However, in the electrolysis method using an electrolytic cell equipped with two or more cation exchange membranes, there was a point at which interpolation occurred, which made it difficult to operate stably and continuously for a long period of time.
例えば、陽極と陰極の間に２枚の陽イオン交換膜を配し
て陽極室、中間室および陰極室の３室に区画した電解槽
においてテトラアルキルアンモニウム塩から高純度の水
酸化テトラアルキルアンモニウムを製造する方法では、
ｌｌＩ極室にテトラアルキルアンモニウム塩、中間室お
よび陰極室に所定の水酸化テトラアルキルアンモニウム
をそれぞれ電解質水溶液として循環供給し通電して、陰
極室より高純度の水酸化テトラアルキルアンモニウムを
取得する。For example, high-purity tetraalkylammonium hydroxide is produced from a tetraalkylammonium salt in an electrolytic cell that is divided into three chambers: an anode chamber, an intermediate chamber, and a cathode chamber by placing two cation exchange membranes between the anode and the cathode. In the manufacturing method,
A tetraalkylammonium salt is supplied to the IlI electrode chamber, and a predetermined tetraalkylammonium hydroxide is circulated as an aqueous electrolyte solution to the intermediate chamber and the cathode chamber, and electricity is applied to obtain highly purified tetraalkylammonium hydroxide from the cathode chamber.
このような３室の電解槽を用い連続運転して水酸化テト
ラアルキルアンモニウムを製造する場合、電解槽の電圧
あるいは温度が上昇しえり、各室への電解質溶液の循環
供給が不安定となるため、ついには運転を停止しなけれ
ばならない状態となる。When producing tetraalkylammonium hydroxide using such a three-chamber electrolytic cell in continuous operation, the voltage or temperature of the electrolytic cell may rise, making the circulating supply of electrolyte solution to each chamber unstable. Eventually, it becomes necessary to stop operation.
本発明者らは、上記の問題点に鑑み鋭意研究した。その
結果、２枚以上の陽イオン交換膜を用いる多室電解槽に
おいて、該陽イオン交換膜の電流効率をそれぞれ特定し
て興なる状態で電解することにより、問題点を解決でき
る知見を得て、本発明を完成するに至ったものである。The present inventors conducted extensive research in view of the above problems. As a result, we obtained knowledge that can solve problems in multichamber electrolyzers that use two or more cation exchange membranes by specifying the current efficiency of each cation exchange membrane and performing electrolysis under the appropriate conditions. , which led to the completion of the present invention.
即ち、本発明は、＠極と陰極との間に２枚以上の陽イオ
ン交換膜を配した電解槽において、陽極側より陰極側へ
順次に該陽イオン交換膜の電流効率を低く維持して電解
することを特徴とする方法である。That is, the present invention provides an electrolytic cell in which two or more cation exchange membranes are disposed between an electrode and a cathode, in which the current efficiency of the cation exchange membranes is maintained low sequentially from the anode side to the cathode side. This method is characterized by electrolysis.
本発明の電解方法において、安定して長期の連続運転を
効率よく達成するためには、Ｉｌｌ極側に電流効率が出
来“るだけ高く、一般に７０％以上の陽イオン交換膜を
用いることが好ましく、また陽極側より陰極側へ隣接し
て配する互の陽イオン交換膜における電流効率の差を一
般に１〜１５％、特に５〜１０％に維持することが好ま
しい。このような本発明に用いる陽イオン交換膜として
は、公知の陽イオン交換膜で特に制限されず、例えばス
ルホン酸基、カルボン酸基などの陽イオン交換基を有す
る炭化水素系あるいはパーフルオロカーボン系の陽イオ
ン交換膜である。In the electrolysis method of the present invention, in order to efficiently achieve stable and long-term continuous operation, it is preferable to use a cation exchange membrane with a current efficiency as high as possible, generally 70% or more, on the Ill electrode side. In addition, it is preferable to maintain the difference in current efficiency between cation exchange membranes arranged adjacently from the anode side to the cathode side generally at 1 to 15%, particularly 5 to 10%. The cation exchange membrane is not particularly limited to known cation exchange membranes, and examples include hydrocarbon-based or perfluorocarbon-based cation exchange membranes having cation exchange groups such as sulfonic acid groups and carboxylic acid groups.
しかして、本発明において、２枚以上の陽イオン交換膜
を陽極側より陰極側へ配した順に低く維持する方法とし
ては、一般にイオン交換容量、含水率など一般に固定イ
オン濃度を調整して電流効率を異にする２枚以上の陽イ
オン交換膜を得て、それぞれ電解槽の電極に所定の関係
位置に配すればよい。なお、各陽イオン交換膜の電流効
率は、該陽イオン交換膜の陰極側に所定濃度の電解質溶
液を供して測定すればよいが、実際に用いる電解槽の構
成および電解条件を勘案して、それぞれ予め所定の電流
効率が決定される。Therefore, in the present invention, the current efficiency is generally maintained by adjusting the fixed ion concentration, such as the ion exchange capacity and water content, in the order in which two or more cation exchange membranes are arranged from the anode side to the cathode side. It is sufficient to obtain two or more cation exchange membranes having different cation exchange membranes and arrange them at predetermined positions relative to the electrodes of the electrolytic cell. The current efficiency of each cation exchange membrane can be measured by applying an electrolyte solution of a predetermined concentration to the cathode side of the cation exchange membrane, but it is possible to measure the current efficiency by applying an electrolyte solution of a predetermined concentration to the cathode side of the cation exchange membrane. Each predetermined current efficiency is determined in advance.
まえ、本発明においては、電流効率が同一である陽イオ
ン交換膜を配した多室電解槽において、該陽イオン交換
膜の陰極側に形成される各室に供給される電解質溶液の
濃度を陰極室側へ順次に高くなるように調節することに
より、該陽イオン交換膜の電流効率を陽極側より陰極側
へ順次に低く維持することができる。例えば、二枚の同
種の陽イオン交換膜により陽極室、中間室および陰極室
に区画された電解槽において、陽極室に原料のテトラア
ルキルアンモニウム塩、中間室および陰極室に水酸化テ
トラアルキルアンモニウムをそれぞれ水溶液として循環
供給して電解し、高純度の水酸化テトラアルキルアンモ
ニウムを陰極室より取得する場合に、陰極室に循環供給
される水酸化テトラアルキルアンモニウム水溶液の温度
を中間室に循環供給される水酸化テトラアルキルアンモ
ニウム水溶液の温度に比べて高く維持する。なお、上記
した水酸化テトラアルキルアンモニウムの製造では、陽
極室におけるテトラアルキルアンモニウム塩水溶液の濃
度を一般に０．５〜５．０規宇、中間室における水酸化
テトラアルキルアンモニウム水溶液の濃度を一般に０．
２〜３．５規定、また陰極室には純水を添加して水酸化
テトラアルキルアンモニウム水溶液の濃度を調整した一
般に０．３〜４．０規定の範囲から選択して採用される
。このとき、前記したように互の陽イオン交換膜におけ
る電流効率の差を１〜１５％とするには、熱極室におけ
る水酸化テトラアルキルアンモニラ鼻水溶液の濃度を中
間室における濃度よりも一般に０．２〜２．．０規定高
くする。同様に、特に電流効率の差を５〜１０第とする
には、一般に０．５〜１．５規定高くする。First, in the present invention, in a multi-chamber electrolytic cell equipped with a cation exchange membrane having the same current efficiency, the concentration of the electrolyte solution supplied to each chamber formed on the cathode side of the cation exchange membrane is adjusted to the cathode side. By adjusting the current efficiency so that it increases successively toward the chamber side, the current efficiency of the cation exchange membrane can be maintained successively lower from the anode side to the cathode side. For example, in an electrolytic cell that is divided into an anode chamber, an intermediate chamber, and a cathode chamber by two cation exchange membranes of the same type, the raw material tetraalkylammonium salt is placed in the anode chamber, and the tetraalkylammonium hydroxide is placed in the intermediate and cathode chambers. When high-purity tetraalkylammonium hydroxide is obtained from the cathode chamber by being circulated and electrolyzed as an aqueous solution, the temperature of the aqueous tetraalkylammonium hydroxide solution that is circulated to the cathode chamber is changed to the temperature of the aqueous solution of tetraalkylammonium hydroxide that is circulated and supplied to the intermediate chamber. The temperature is maintained higher than that of the aqueous tetraalkylammonium hydroxide solution. In the production of the above-mentioned tetraalkylammonium hydroxide, the concentration of the aqueous tetraalkylammonium salt solution in the anode chamber is generally 0.5 to 5.0 K, and the concentration of the aqueous tetraalkylammonium hydroxide solution in the intermediate chamber is generally 0.5 - 5.0 K.
The concentration of the tetraalkylammonium hydroxide aqueous solution is adjusted by adding pure water to the cathode chamber, and the concentration is generally selected from the range of 0.3 to 4.0N. At this time, in order to make the difference in current efficiency between the two cation exchange membranes 1 to 15% as described above, the concentration of the tetraalkyl ammonium hydroxide snot solution in the hot electrode chamber is generally lower than the concentration in the intermediate chamber. 0.2-2. ．． 0 regulation higher. Similarly, in order to specifically increase the difference in current efficiency by 5 to 10 orders, the current efficiency is generally increased by 0.5 to 1.5 normals.
なお、本発明により、例えば水酸化テトラアルキルアン
モニウムなどを製造する場合には、陽極の腐食、陽極室
における副反応を防止するために、陽極と陽極側の陽イ
オン交換膜との間に陰イオン交換膜を配した電解槽を用
いて、陽極室に酸水溶液を供給する方法が好ましい。さ
らに、陽極における有形なハロゲンガスの発生、あるい
は上記の電解槽において陰イオン交換膜の劣化を防止す
るために、該陰イオン交換膜の陽極側に耐拳化性の陽イ
オン交換膜を配する態様も好ましい。In addition, when producing, for example, tetraalkylammonium hydroxide according to the present invention, in order to prevent corrosion of the anode and side reactions in the anode chamber, anions are placed between the anode and the cation exchange membrane on the anode side. A preferred method is to supply an acid aqueous solution to the anode chamber using an electrolytic cell equipped with an exchange membrane. Furthermore, in order to prevent the generation of tangible halogen gas at the anode or the deterioration of the anion exchange membrane in the electrolytic cell, a cation exchange membrane that is resistant to curing is placed on the anode side of the anion exchange membrane. The aspect is also preferable.
本発明の電解方法について、代表的にテトラアルキルア
ンモニウム塩から水酸化テトラアルキルアンモニウムの
製造を例示したが、その峰か例えば、シュウ酸からグリ
オキシル酸、シスチンからシスティン、ニトロ基含有芳
香族化合物からアミ７基含有芳香族化合物などの製造に
適用することができる。Regarding the electrolytic method of the present invention, the production of tetraalkylammonium hydroxide from a tetraalkylammonium salt has been exemplified as a representative example, but the most important examples are, for example, glyoxylic acid from oxalic acid, cystine from cystine, amino acid from nitro group-containing aromatic compound, etc. It can be applied to the production of 7-group-containing aromatic compounds.
イオン交換膜は、一般に使用時間の経過にっれて劣化し
て、その電流効率が次第に低下する。Ion exchange membranes generally deteriorate over time and their current efficiency gradually decreases.
前記したような２＆の陽イオン交換族を配して陽極室、
中間室および陰極室の３室に区画された電解槽を使用し
て水酸化テトラアルキルアンモニウムを製造する場合に
は、両陽イオン交換膜の劣化速度が異なり電流効率に差
を生じてくる。即ち、原料のテトラアルキルアンモニウ
ム塩に含まれる不純物のため、該テトラアルキルアンモ
ニウム塩の水溶液を供給するａｅｉ室を区画している陽
イオン交換膜の方が、陰極室を区画している陽イオン交
換膜よりも速く劣化し電流効率も速く低下する場合が多
い。An anode chamber with a cation exchange group of 2& as described above,
When producing tetraalkylammonium hydroxide using an electrolytic cell divided into three chambers, an intermediate chamber and a cathode chamber, the deterioration rates of both cation exchange membranes are different, resulting in a difference in current efficiency. That is, because of the impurities contained in the raw material tetraalkylammonium salt, the cation exchange membrane that partitions the aei chamber that supplies the aqueous solution of the tetraalkylammonium salt is better than the cation exchange membrane that partitions the cathode chamber. In many cases, they deteriorate faster than membranes, and their current efficiency also decreases faster.
このような状態の電解槽において、陽極室から中間室を
騒て陰極室へそれぞれ陽イオン交換膜を介して移動する
テトラアルキルアンモニウムイオンは、陰極室へ向かっ
て中間室から出てゆく量が、陽極室から中間室へ入って
くる量に比べて多くなるため、中間室のテトラアルキル
アアンモニウムイオンが次第に減少する傾向になる。こ
の中間室におけるテトラアルキルアンモニウムイオンの
減少により、該中間室にｌ！環供給される水酸化テトラ
アルキルアンモニウム水溶液における水酸化テトラアル
キルアンモニウムの当量数は減少する。また、テトラア
ルキルアンモニウムイオンは、通常４分子程度の水分子
を同伴するため、中間室に循環供給される水酸化テトラ
アルキルアンモニウム水溶液の液量も、テトラアルキル
アンモニウムイオンの減少に伴つて減少していくことに
なる。このような中間室にＷＨ４供給される水酸化テト
ラアルキルアンモニウム水溶液における水酸化テトラア
ルキルアンモニウムの当量数あるいは液量が減少する結
果、各室への溶液の循環供給が不安定になるとともに、
摺電圧および温度が上昇する問題を招き、ひいては電解
運転を停止せざるを得ない状態に至る。In an electrolytic cell in such a state, the amount of tetraalkylammonium ions that move from the anode chamber to the intermediate chamber and then to the cathode chamber via the cation exchange membranes is as follows: The amount of tetraalkyl ammonium ions in the intermediate chamber tends to gradually decrease because the amount increases compared to the amount entering the intermediate chamber from the anode chamber. This decrease in tetraalkylammonium ions in the intermediate chamber causes l! The number of equivalents of tetraalkylammonium hydroxide in the ring-supplied aqueous tetraalkylammonium hydroxide solution decreases. In addition, since tetraalkylammonium ions are usually accompanied by about 4 water molecules, the amount of the tetraalkylammonium hydroxide aqueous solution that is circulated and supplied to the intermediate chamber also decreases as the tetraalkylammonium ions decrease. I'm going to go. As a result of a decrease in the number of equivalents or the amount of tetraalkylammonium hydroxide in the tetraalkylammonium hydroxide aqueous solution supplied to the intermediate chamber, the circulating supply of the solution to each chamber becomes unstable, and
This results in a problem of increased sliding voltage and temperature, which eventually leads to a situation where the electrolytic operation has to be stopped.
これに対して、本発明の電解方法によれば、電解槽に配
した２枚以上の陽イオン交換膜について、それぞれ互に
所定の電流効率を維持させることにより、上記した如き
従来法における問題が解消し、長期に安定した連続運転
を可能にしたものである。On the other hand, according to the electrolysis method of the present invention, two or more cation exchange membranes arranged in an electrolytic cell each maintain a predetermined current efficiency, thereby solving the problems of the conventional method as described above. This has enabled stable continuous operation over a long period of time.
以下、本発明の代表的な実施例を拳ぜて説明するが、本
発明はこれに制限される吃のでない。Hereinafter, typical embodiments of the present invention will be described in detail, but the present invention is not limited thereto.
実施例１
陽極と陸標との間に、＠極側より順に陰イオン交換Ｉ４
（徳山曹達社製、ネオセプタＡＭ−１）。Example 1 Anion exchange I4 was applied between the anode and the landmark in order from the @ pole side.
(Neosepta AM-1, manufactured by Tokuyama Soda Co., Ltd.).
陽イオン交換ＩＩＩおよび陽イオン交換膜２（いずれも
徳山曹達社製、ネオセプタ０６６−１０？）をそれぞれ
配して、ｌｉＩ極室、陰イオン交ａｍと陽イオン交換膜
１とにより区画された中間室１゜陽イオン交換Ｉｌｌと
陽イオン交換膜２とにより区画された中間室２および陰
極室からなる有効通電面積２１１１１”の４室電解檜を
構成した。なお、ａｉａｉには白金をコーティングした
チタン板、陰極にはニッケルを用いた。A cation exchange III and a cation exchange membrane 2 (both manufactured by Tokuyama Soda Co., Ltd., NeoSepta 066-10?) are arranged, respectively, and an intermediate electrode chamber partitioned by a liI electrode chamber, an anion exchange chamber and a cation exchange membrane 1 is provided. A four-chamber electrolysis chamber with an effective current-carrying area of 21111'' was constructed, consisting of an intermediate chamber 2 and a cathode chamber partitioned by a cation exchange chamber 1 and a cation exchange membrane 2. Nickel was used for the plate and cathode.
上記の４室電解槽を用いて、陽極室に０．５規定の塩醗
、中間室１に１．５９．定のテトラメチルアンモニラム
ク關うイド水溶液、中間ｇ１２に１．６規定の水酸化テ
トラメチルアンモニウム水溶液および陰極室に１．８規
定の水酸化テトラメチルアンモニウム水溶液をそれぞれ
外部のタンクを介して線速度１０ ａｍ ／ ｓｅａで
循環供給し、電流密度２０Ａ／ａｍ／で電解し陰極室か
ら高純度の水酸化テトラメチルアンモニウムを生成し取
得した。なお、陰極室における水酸化テトラメチルアン
モニウム水溶液の濃度を１．８ｆＩＬ定に維持するため
に、純水を加えて調節した。Using the above four-chamber electrolytic cell, the anode chamber contains 0.5 N of salt and the intermediate chamber 1 contains 1.59 N of salt. A 1.6N aqueous tetramethylammonium hydroxide solution was added to the intermediate g12, and a 1.8N aqueous tetramethylammonium hydroxide solution was added to the cathode chamber through external tanks. High purity tetramethylammonium hydroxide was produced and obtained from the cathode chamber by circulating supply at a rate of 10 am/sea and electrolyzing at a current density of 20 A/am/. In addition, in order to maintain the concentration of the tetramethylammonium hydroxide aqueous solution in the cathode chamber at a constant value of 1.8 fIL, pure water was added to adjust the concentration.
その結果、２ケ月間の連続運転を実施したが、摺電圧は
２３７の略一定であり、を喪中間室２に循環供給される
水酸化テトラメチルアンモニウム水溶液の液量は少し増
加しただけであり、さらに安定して運転を続行すること
も可能であった。 なお、上記の電解における陽イオン
交換膜１および陽イオン交換膜２のそれぞれ電流効率は
、陽極と陰極との間に陽イオン交換Ｉ！１１あるいは陽
イオン交換膜２として使用される陽イオン交換膜ネオセ
プタ０６６−１０νを配して、陰極室および陰極室から
なる有効通電面＠ ０．２ ＋１１１’の２室電解槽を
構成して測定した。すなわち、まず陽極室に１．５規定
のテトラメチルアンモニウムクロライド水溶液、陰極室
に０．５規定の水酸化テトラメチルアンモニウム水溶液
をそれぞれ満たし、電流密度２０ム／ｄｗＩで１時間電
解した。電解終了後、陰極室に個たした水酸化テトラメ
チルアンモニウム水溶液の濃度を測定し、電解の前後に
おける水酸化テトラメチルアンモニウム水溶液の濃度差
から電流効率を得た。同様に、陰極室に満たす水酸化テ
トラメチルアンモニウム水溶液の濃度を１．０．１．５
．２．０規定として電解を行い、それぞれの電解につい
て陽イオン交換膜の電流効率を得た。次いで、それぞれ
の電解における水酸化テトラメチルアンモニウム水溶液
の平均濃度と電流効率との間の関係をグラフに表した。As a result, although continuous operation was carried out for two months, the sliding voltage was approximately constant at 237, and the amount of the tetramethylammonium hydroxide aqueous solution circulated and supplied to the mourning intermediate chamber 2 increased only slightly. It was also possible to continue driving more stably. In addition, the current efficiency of the cation exchange membrane 1 and the cation exchange membrane 2 in the above electrolysis is the cation exchange I! between the anode and the cathode. 11 or the cation exchange membrane Neoceptor 066-10ν used as the cation exchange membrane 2 to form a two-chamber electrolytic cell with an effective current-carrying surface @ 0.2 +111' consisting of a cathode chamber and a cathode chamber. did. That is, first, the anode chamber was filled with a 1.5N aqueous solution of tetramethylammonium chloride, and the cathode chamber was filled with a 0.5N aqueous solution of tetramethylammonium hydroxide, and electrolysis was carried out at a current density of 20 μm/dwI for 1 hour. After the electrolysis was completed, the concentration of the tetramethylammonium hydroxide aqueous solution placed in the cathode chamber was measured, and the current efficiency was obtained from the concentration difference of the tetramethylammonium hydroxide aqueous solution before and after electrolysis. Similarly, the concentration of the tetramethylammonium hydroxide aqueous solution filled in the cathode chamber was set to 1.0.1.5.
．． Electrolysis was performed under a normal setting of 2.0, and the current efficiency of the cation exchange membrane was obtained for each electrolysis. Next, the relationship between the average concentration of the tetramethylammonium hydroxide aqueous solution and the current efficiency in each electrolysis was expressed in a graph.
ここで、水酸化テトラメチルアンモニウム水溶液の平均
濃度とは、電解の開始時における濃度と電解終了時にお
ける濃度の平均値である。このように作成したグラフか
ら、水酸化テトラメチルアンモニウム水溶液の濃度が１
．６規宏のときの陽イオン交換膜ネオセプタ０６６−１
０ｙの電流効率はフ３襲であり、１．８規定のときの電
流効率は６７％であった。Here, the average concentration of the tetramethylammonium hydroxide aqueous solution is the average value of the concentration at the start of electrolysis and the concentration at the end of electrolysis. From the graph created in this way, the concentration of the tetramethylammonium hydroxide aqueous solution is 1
．． Cation exchange membrane Neocepta 066-1 at the time of 6 Norihiro
The current efficiency at 0y was F3, and the current efficiency at 1.8 regulation was 67%.
比較例１
実施例１において、中間室２に供給される水酸化テトラ
メチルアンモニウム水溶液の濃度を１．８規定として、
陰極室における水酸化テトラメチルアンモニウム水溶液
の濃度に一致させたこと以外は、実施例１と同一の条件
で電解槽を運転した。運転開始の２日後から、電槽電圧
が上昇し始め、運転開始時には２３Ｖであった電槽電圧
が運転開始から１週間後には３２７にまで上昇し、また
電解槽の温度も、運転開始時の３５℃から５２℃に上昇
したため、電解槽の運転を停止した。Comparative Example 1 In Example 1, the concentration of the tetramethylammonium hydroxide aqueous solution supplied to the intermediate chamber 2 was set to 1.8N,
The electrolytic cell was operated under the same conditions as in Example 1, except that the concentration was made to match the concentration of the aqueous tetramethylammonium hydroxide solution in the cathode chamber. Two days after the start of operation, the cell voltage began to rise, and the cell voltage, which was 23V at the start of operation, rose to 327V one week after the start of operation, and the temperature of the electrolytic cell also changed to the same level as at the start of operation. Since the temperature rose from 35°C to 52°C, operation of the electrolytic cell was stopped.
実施例２
実施例１において、陽イオン交換Ｊ１１！１としてネオ
セプタ０６６−１０１の代りにデＡメン社製のＩａｆｉ
ａｎ ９０１ （パーフルオロ系陽イオン交換膜）を該
膜のカルボン醗層を有する面を陰極側に向けて配した。Example 2 In Example 1, Iafi manufactured by DeAmen Co., Ltd. was used instead of Neocepta 066-101 as the cation exchange J11!1.
An 901 (perfluorinated cation exchange membrane) was arranged with the surface of the membrane having the carbon layer facing the cathode side.
また、陽極室には０．５規定の塩酸、中間室１には２．
５規定の炭酸テトラメチルアンモニウム水溶液、中間室
２および陰極室にはそれぞれ２．０規定の水酸化テトラ
メチルアンモニウム水溶液をそれぞれ循環供給した。In addition, 0.5 N hydrochloric acid was placed in the anode chamber, and 2.0 N hydrochloric acid was placed in the intermediate chamber 1.
A 5N aqueous solution of tetramethylammonium carbonate and a 2.0N aqueous solution of tetramethylammonium hydroxide were supplied in circulation to the intermediate chamber 2 and the cathode chamber, respectively.
なお、陰極室には循環供給される水酸化テトラメチルア
ンモニウム水溶液の濃度を２．０規定とするために純水
を加えた。その他の条件は実施例１と同一にして電解を
行つた。陽イオン交換膜１として使用した！１ａｆｉｏ
ｎ ９０１の電流効率は、陰極側の面に接触する水酸化
テトラメチルアンモニウム水溶液における水酸化テトラ
メチルアンモニウムの濃度が２．０規定であるとき、連
続運転したが、中間室２にａｍ供給される水酸化テトラ
メチルアンモニウム水溶液の液量がわずかばかり増加し
ただけであり、摺電圧も２３Ｖの略一定であり、温度の
変化もなく、さらに電解槽の運転を続行することも可能
であった。Note that pure water was added to the cathode chamber in order to adjust the concentration of the tetramethylammonium hydroxide aqueous solution that was circulated to 2.0 normal. Other conditions were the same as in Example 1 to carry out electrolysis. Used as cation exchange membrane 1! 1afio
The current efficiency of n901 was determined by continuous operation when the concentration of tetramethylammonium hydroxide in the tetramethylammonium hydroxide aqueous solution in contact with the cathode side surface was 2.0 normal, but am supplied to intermediate chamber 2. The amount of the aqueous tetramethylammonium hydroxide solution increased only slightly, the sliding voltage remained approximately constant at 23 V, there was no change in temperature, and it was possible to continue operation of the electrolytic cell.
比較例２
実施例２において、陽イオン交換膜１としてネオ七ブタ
０６６−１０７％陽イオン交換膜２としてＮ亀ｆｉｏｎ
９０１を使用したこと以外は、実施例２と同一の条件で
電解を実施した。Comparative Example 2 In Example 2, Neo Shichibuta 066-107 was used as the cation exchange membrane 1, and N Kamefion was used as the cation exchange membrane 2.
Electrolysis was carried out under the same conditions as in Example 2, except that 901 was used.
その結果、運転開始の直後より中間室２に循環供給され
る水酸化テトラメチルアンモニウム水溶液の液量が減少
し、１週間後には水酸化テトラメチルアンモニウム水溶
液を安定して供給することができなくなりたため、電解
槽の運転を停止し九。As a result, the amount of the tetramethylammonium hydroxide aqueous solution that was circulated and supplied to the intermediate chamber 2 decreased immediately after the start of operation, and after one week, it became impossible to stably supply the tetramethylammonium hydroxide aqueous solution. 9. Stop the operation of the electrolyzer.
Claims (2)
配した電解槽において、陽極側より陰極側へ順次に該陽
イオン交換膜の電流効率を低く維持することを特徴とす
る電解方法。(1) In an electrolytic cell in which two or more cation exchange membranes are arranged between an anode and a cathode, the current efficiency of the cation exchange membranes is maintained low sequentially from the anode side to the cathode side. Electrolysis method.
アルキルアンモニウムを製造する特許請求の範囲第（１
）項記載の電解方法。(2) Claim No. 1 for producing tetraalkylammonium hydroxide from a tetraalkylammonium salt
) The electrolysis method described in section 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63266017A JP2584846B2 (en) | 1988-10-24 | 1988-10-24 | Method for producing tetraalkylammonium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63266017A JP2584846B2 (en) | 1988-10-24 | 1988-10-24 | Method for producing tetraalkylammonium hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02115387A true JPH02115387A (en) | 1990-04-27 |
| JP2584846B2 JP2584846B2 (en) | 1997-02-26 |
Family
ID=17425219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63266017A Expired - Lifetime JP2584846B2 (en) | 1988-10-24 | 1988-10-24 | Method for producing tetraalkylammonium hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2584846B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108396327A (en) * | 2018-05-23 | 2018-08-14 | 梁小朝 | A kind of device and method of continuity method production tetramethylammonium hydroxide |
| CN110318066A (en) * | 2019-06-20 | 2019-10-11 | 青岛鼎海电化学科技有限公司 | A kind of preparation method of tetra-alkyl ammonium hydroxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56123386A (en) * | 1980-03-03 | 1981-09-28 | Konosuke Kishida | Method and apparatus for electrolysis of salt |
| JPS59211582A (en) * | 1983-05-17 | 1984-11-30 | Toagosei Chem Ind Co Ltd | Production of aqueous caustic alkali solution having high purity |
| JPS60131986A (en) * | 1983-12-19 | 1985-07-13 | Showa Denko Kk | Manufacture of quaternary ammonium hydroxide of high purity |
-
1988
- 1988-10-24 JP JP63266017A patent/JP2584846B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56123386A (en) * | 1980-03-03 | 1981-09-28 | Konosuke Kishida | Method and apparatus for electrolysis of salt |
| JPS59211582A (en) * | 1983-05-17 | 1984-11-30 | Toagosei Chem Ind Co Ltd | Production of aqueous caustic alkali solution having high purity |
| JPS60131986A (en) * | 1983-12-19 | 1985-07-13 | Showa Denko Kk | Manufacture of quaternary ammonium hydroxide of high purity |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108396327A (en) * | 2018-05-23 | 2018-08-14 | 梁小朝 | A kind of device and method of continuity method production tetramethylammonium hydroxide |
| CN108396327B (en) * | 2018-05-23 | 2024-04-09 | 柏川新材料科技(宁波)有限公司 | Equipment and method for producing tetramethyl ammonium hydroxide by continuous method |
| CN110318066A (en) * | 2019-06-20 | 2019-10-11 | 青岛鼎海电化学科技有限公司 | A kind of preparation method of tetra-alkyl ammonium hydroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2584846B2 (en) | 1997-02-26 |
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