JP3260145B2 - Method for producing quaternary ammonium hydroxide aqueous solution - Google Patents
Method for producing quaternary ammonium hydroxide aqueous solutionInfo
- Publication number
- JP3260145B2 JP3260145B2 JP11197991A JP11197991A JP3260145B2 JP 3260145 B2 JP3260145 B2 JP 3260145B2 JP 11197991 A JP11197991 A JP 11197991A JP 11197991 A JP11197991 A JP 11197991A JP 3260145 B2 JP3260145 B2 JP 3260145B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- quaternary ammonium
- ammonium hydroxide
- tetramethylammonium
- methanol
- 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.)
- Expired - Lifetime
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水酸化第四アンモニウ
ム水溶液の製造方法に関する。The present invention relates to a method for producing a quaternary ammonium hydroxide aqueous solution.
【０００２】[0002]
【従来の技術】第３級アミンと炭酸エステルとの反応に
よつて炭酸ジテトラアルキルアンモニウムを得、その水
溶液を電気分解して、水酸化第四アンモニウム水溶液を
得ることは、例えば、特開昭６３−２４０８０号公報に
記載されているように知られている。2. Description of the Related Art Ditetraalkylammonium carbonate is obtained by reacting a tertiary amine with a carbonate, and an aqueous solution thereof is electrolyzed to obtain a quaternary ammonium hydroxide aqueous solution. It is known as described in JP 63-24080.
【０００３】しかし、上記した方法を含む従来の方法に
よつて、炭酸水素テトラメチルアンモニウムを得、その
水溶液を電気分解して、水酸化第四アンモニウム水溶液
を得るとき、電極や交換膜が短時間に損傷する。However, when tetramethylammonium hydrogencarbonate is obtained by a conventional method including the above-mentioned method, and the aqueous solution is electrolyzed to obtain a quaternary ammonium hydroxide aqueous solution, the electrodes and the exchange membrane are short-lived. To be damaged.
【０００４】[0004]
【発明が解決しようとする課題】本発明者らは、従来の
水酸化第四アンモニウム水溶液の製造における上記した
問題を解決するために鋭意研究した結果、電気分解に用
いる炭酸水素テトラメチルアンモニウム水溶液中のメタ
ノールを微量に抑えることによつて、電極や隔膜の損傷
なしに、長時間にわたつて、炭酸水素テトラメチルアン
モニウム水溶液の電気分解を行なうことができることを
見出して、本発明に至つたものである。SUMMARY OF THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned problems in the production of a conventional quaternary ammonium hydroxide aqueous solution. It has been found that by suppressing the amount of methanol in a trace amount, it is possible to electrolyze an aqueous solution of tetramethylammonium hydrogencarbonate for a long period of time without damaging the electrodes and the diaphragm, leading to the present invention. is there.
【０００５】[0005]
【課題を解決するための手段】本発明による水酸化第四
アンモニウム水溶液の製造は、主成分としての炭酸水素
テトラメチルアンモニウムと共に、メタノールを含む水
溶液を電気分解して水酸化第四アンモニウム水溶液を製
造する方法において、メタノール含量を１００ppm 以下
とした上記水溶液を電気分解に供することを特徴とす
る。According to the present invention, a quaternary ammonium hydroxide aqueous solution is produced by electrolyzing an aqueous solution containing methanol together with tetramethylammonium hydrogencarbonate as a main component. Wherein the aqueous solution having a methanol content of 100 ppm or less is subjected to electrolysis.
【０００６】特に、本発明の方法は、好ましくは、炭酸
ジメチルとトリメチルアミンとをメタノールの存在下で
反応させて炭酸テトラメチルアンモニウムメチルを含む
反応混合物を得、この反応混合物に水を加え、炭酸テト
ラメチルアンモニウムメチルを加水分解して、主成分と
して炭酸水素テトラメチルアンモニウムを含むと共にメ
タノール１００ppm 以下を含む水溶液を得、これを水で
希釈し、電気分解することを特徴とする。[0006] In particular, the method of the present invention, preferably, the dimethyl carbonate and trimethylamine are reacted in the presence of methanol to obtain a reaction mixture containing carbonate tetramethylammonium methyl, water was added to the reaction mixture, carbon tetra It is characterized by hydrolyzing methylammonium methyl to obtain an aqueous solution containing tetramethylammonium hydrogencarbonate as a main component and containing 100 ppm or less of methanol, and diluting this with water for electrolysis.
【０００７】本発明の方法において、炭酸テトラメチル
アンモニウムメチルを含む反応混合物は、炭酸ジメチル
とトリメチルアミンとをメタノールの存在下で反応させ
ることによつて得られる。トリメチルアミンは、通常、
炭酸ジメチルに対して0.８〜３モル比の範囲で用いら
れ、また、反応溶剤としてのメタノールは、通常、炭酸
ジメチルに対する重量比にて５以下、好ましくは0.５〜
2.０の範囲で用いられる。反応は、常圧又は加圧下、好
ましくは密閉系で６０〜１８０℃、好ましくは８０〜１
５０℃で0.５〜１０時間、好ましくは２〜６時間行なわ
れる。反応方式は、バツチ方式によつてもよく、また、
炭酸ジメチルのメタノール溶液中にトリメチルアミンを
連続的に供給する部分連続方式によつてもよい。In the method of the present invention, a reaction mixture containing tetramethylammonium methyl carbonate is obtained by reacting dimethyl carbonate with trimethylamine in the presence of methanol. Trimethylamine is usually
It is used in a range of 0.8 to 3 mole ratio to dimethyl carbonate, and methanol as a reaction solvent is usually 5 or less in weight ratio to dimethyl carbonate, preferably 0.5 to 0.5.
Used in the range of 2.0. The reaction is carried out at normal pressure or under pressure, preferably in a closed system at 60 to 180 ° C, preferably 80 to 1 ° C.
The reaction is carried out at 50 ° C. for 0.5 to 10 hours, preferably 2 to 6 hours. The reaction system may be a batch system,
A partial continuous system in which trimethylamine is continuously supplied into a methanol solution of dimethyl carbonate may be used.
【０００８】次いで、本発明の方法によれば、このよう
にして得られた炭酸テトラメチルアンモニウムメチルを
含む反応混合物に超純水を加え、次いで、好ましくは減
圧下に、上記反応混合物からメタノール、トリメチルア
ミン及び水を留去しつつ、炭酸テトラメチルアンモニウ
ムメチルを炭酸水素テトラメチルアンモニウムに加水分
解して、メタノールを１００ppm 以下、好ましくは５０
ppm 以下、特に好ましくは２０ppm 以下の範囲で含むと
共に、主成分として炭酸水素テトラメチルアンモニウム
を含む水溶液を得る。この加水分解反応においては、超
純水は、炭酸テトラメチルアンモニウムメチルに対し
て、１〜５０モル比、好ましくは５〜２０モル比の範囲
で用いられる。反応時間は、通常、１０分乃至２０時
間、好ましくは0.５〜１０時間である。上記水溶液は、
炭酸水素テトラメチルアンモニウムを３０重量％以上含
むことが望ましい。Next, according to the method of the present invention, ultrapure water is added to the reaction mixture thus obtained containing tetramethylammonium methyl carbonate, and then methanol, Trimethyla
Mineral and water are distilled off, and tetramethylammonium carbonate
Water to tetramethylammonium bicarbonate
In other words , methanol is less than 100 ppm, preferably 50 ppm.
An aqueous solution containing not more than 20 ppm, particularly preferably not more than 20 ppm, and containing tetramethylammonium hydrogencarbonate as a main component is obtained. In this hydrolysis reaction, ultrapure water is used in a molar ratio of 1 to 50, preferably 5 to 20 with respect to tetramethylammonium methyl carbonate. The reaction time is generally 10 minutes to 20 hours, preferably 0.5 to 10 hours. The aqueous solution is
It is desirable to contain 30% by weight or more of tetramethylammonium hydrogen carbonate.
【０００９】このようにして得られた炭酸水素テトラメ
チルアンモニウムを主成分として含む水溶液を超純水に
て適宜濃度に希釈し、これを常法に従つて電気分解すれ
ば、水酸化第四アンモニウム水溶液を得る。本発明の方
法によれば、炭酸水素テトラメチルアンモニウムを主成
分として含む水溶液は、炭酸水素テトラメチルアンモニ
ウムと共に少量の炭酸ジテトラメチルアンモニウムを含
む。この炭酸ジテトラメチルアンモニウムは、前記反応
混合物を脱メタノールする際に、少量が副生し、また、
炭酸ジメチルとトリメチルアミンとの反応においても、
微量が副生するとみられる。The thus obtained aqueous solution containing tetramethylammonium bicarbonate as a main component is appropriately diluted with ultrapure water and electrolyzed according to a conventional method to obtain quaternary ammonium hydroxide. An aqueous solution is obtained. According to the method of the present invention, the aqueous solution containing tetramethylammonium hydrogen carbonate as a main component contains a small amount of ditetramethylammonium carbonate together with tetramethylammonium hydrogencarbonate. This ditetramethyl ammonium carbonate is by-produced in a small amount when the reaction mixture is demethanolized,
In the reaction between dimethyl carbonate and trimethylamine,
A small amount is expected to be a by-product.
【００１０】しかしながら、この炭酸ジテトラメチルア
ンモニウムは、前記炭酸水素テトラメチルアンモニウム
の加水分解時、加水分解されないが、炭酸水素テトラメ
チルアンモニウムの電気分解時には、同時に加水分解さ
れて、水酸化第四アンモニウムを与える。従つて、本発
明の方法によれば、高収率にて目的とする水酸化第四ア
ンモニウムを得ることができる。However, this ditetramethylammonium carbonate is not hydrolyzed when the above-mentioned tetramethylammonium hydrogencarbonate is hydrolyzed, but is hydrolyzed at the same time when the tetramethylammonium hydrogencarbonate is electrolyzed to give quaternary ammonium hydroxide. give. Therefore, according to the method of the present invention, the desired quaternary ammonium hydroxide can be obtained in high yield.
【００１１】本発明においては、炭酸水素テトラメチル
アンモニウムの電気分解は、隔膜によつて隔てられた陰
極室と陽極室とを備えた電解槽を用いて、電解槽の陰極
室内に例えば１〜５％程度の水酸化第四アンモニウム水
溶液を循環させると共に、陽極室内に５〜３０％程度の
炭酸水素テトラメチルアンモニウム水溶液を循環させな
がら、電流密度５〜３０Ａ／dm2 の条件で直流電圧を印
加して電気分解を行なう。電気分解の進行に伴つて陽極
室には炭酸水素テトラメチルアンモニウムを補充し、陰
極室の水酸化第四アンモニウム水溶液を抜き出せば、連
続して電気分解を行なうことができる。In the present invention, the electrolysis of tetramethylammonium bicarbonate is carried out by using an electrolytic cell having a cathode chamber and an anode chamber separated by a diaphragm, for example, in the cathode chamber of the electrolytic cell. % Of a quaternary ammonium hydroxide aqueous solution while circulating a 5-30% aqueous solution of tetramethylammonium bicarbonate in the anode chamber while applying a DC voltage at a current density of 5-30 A / dm 2. To perform electrolysis. As the electrolysis proceeds, the anode chamber is replenished with tetramethylammonium hydrogencarbonate, and the aqueous solution of quaternary ammonium hydroxide in the cathode chamber is withdrawn, whereby the electrolysis can be performed continuously.
【００１２】[0012]
【発明の効果】以上のように、本発明の方法によれば、
炭酸ジメチルとトリメチルアミンとをメタノールの存在
下で反応させて炭酸テトラメチルアンモニウムメチルを
含む反応混合物を得、この反応混合物に水を加え、減圧
下にメタノール及びトリメチルアミンを留去しつつ、炭
酸テトラメチルアンモニウムメチルを加水分解して、メ
タノール１００ppm 以下を含む炭酸水素テトラメチルア
ンモニウムを得、その水溶液を電気分解するとき、電極
や隔膜の損傷なしに、長時間にわたつて電気分解するこ
とができる。As described above, according to the method of the present invention,
Dimethyl carbonate and trimethylamine are reacted in the presence of methanol to obtain a reaction mixture containing tetramethylammonium methyl carbonate, water is added to the reaction mixture, and while methanol and trimethylamine are distilled off under reduced pressure, tetramethylammonium carbonate is removed. Methyl is hydrolyzed to obtain tetramethylammonium hydrogen carbonate containing 100 ppm or less of methanol, and when the aqueous solution is electrolyzed, the electrolysis can be performed for a long time without damaging the electrodes and the diaphragm.
【００１３】[0013]
実施例１ 炭酸ジメチル１９０ｇ（2.１モル）、トリメチルアミン
１２４ｇ（2.１モル）及びメタノール１９０ｇを反応器
内に仕込み、１２５℃で３時間反応させた。反応終了
後、得られた反応混合物に超純水７６０ｇ（４2.２２モ
ル）を加え、減圧下にメタノール、トリメチルアミン及
び水を留去した。このようにして得られた水溶液４５5.
９ｇ中の炭酸水素テトラメチルアンモニウムは４０重量
％、炭酸ジテトラメチルアンモニウムは１２重量％及び
メタノール量は２０ppm であつた。この水溶液を超純水
で炭酸水素テトラメチルアンモニウム濃度１５％に希釈
し、電気分解に供した。Example 1 190 g (2.1 mol) of dimethyl carbonate, 124 g (2.1 mol) of trimethylamine and 190 g of methanol were charged in a reactor and reacted at 125 ° C. for 3 hours. After the reaction was completed, 760 g (42.22 mol) of ultrapure water was added to the obtained reaction mixture, and methanol, trimethylamine and water were distilled off under reduced pressure. The aqueous solution 455 thus obtained.
In 9 g, tetramethylammonium hydrogencarbonate was 40% by weight, ditetramethylammonium carbonate was 12% by weight, and the amount of methanol was 20 ppm. This aqueous solution was diluted with ultrapure water to a concentration of tetramethylammonium bicarbonate of 15% and subjected to electrolysis.
【００１４】用いた電解槽は、白金属金属酸化物被覆チ
タンからなる陽極とニツケルからなる陰極とナフイオン
膜（デユポン社製）を備えたもので、この電解槽の陽極
室内に上記濃度１５％の炭酸水素テトラメチルアンモニ
ウム水溶液を滞留時間１０秒にて循環させ、陰極室内に
濃度５％の第四水酸化アンモニウム水溶液を滞留時間１
８秒にて循環させながら、陰極と陽極との間に電圧１５
Ｖ、電流密度３０Ａ／dm2 の直流電圧を印加し、陽極室
には炭酸水素テトラメチルアンモニウム水溶液を補充
し、陰極室からはそれに見合う量を抜き出した。その結
果、８０００時間経過後も、電圧に異常な上昇なく、電
極及び隔膜にも異常は認められなかつた。The electrolytic cell used was provided with an anode made of white metal oxide coated titanium, a cathode made of nickel, and a naphion membrane (manufactured by DuPont). An aqueous solution of tetramethylammonium hydrogen carbonate is circulated for a residence time of 10 seconds, and a quaternary ammonium hydroxide aqueous solution having a concentration of 5% is retained in the cathode chamber for a residence time of 1 second.
While circulating for 8 seconds, a voltage of 15 was applied between the cathode and the anode.
V, a DC voltage of a current density of 30 A / dm 2 was applied, an aqueous solution of tetramethylammonium bicarbonate was replenished in the anode compartment, and an appropriate amount was extracted from the cathode compartment. As a result, even after 8000 hours, there was no abnormal increase in the voltage and no abnormality in the electrodes and the diaphragm.
【００１５】尚、電極の寿命とは、電圧が急激に上昇
し、電極に剥離に発生するまでの時間をいう。 比較例１ 実施例１において、反応終了後、超純水を３００ｇとし
た以外は、実施例１と同様にして、濃度６０％の炭酸水
素テトラメチルアンモニウム水溶液を得た。メタノール
量は１４０００ppm であつた。The term "life of the electrode" means the time required for the voltage to rise sharply and for the electrode to peel off. Comparative Example 1 A 60% aqueous solution of tetramethylammonium hydrogen carbonate was obtained in the same manner as in Example 1, except that 300 g of ultrapure water was used after the completion of the reaction. The amount of methanol was 14000 ppm.
【００１６】この炭酸水素テトラメチルアンモニウム水
溶液を実施例１と同じ条件下に電気分解したところ、１
３５０時間後に電圧の急激な上昇が認められたので、電
気分解を中断した。電極及び隔膜に剥離が認められた。When this aqueous solution of tetramethylammonium hydrogen carbonate was electrolyzed under the same conditions as in Example 1,
After 350 hours, a sharp increase in voltage was observed, so the electrolysis was stopped. Peeling was observed on the electrode and the diaphragm.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−93752（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C25B 1/00 - 15/08 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-93752 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C25B 1/00-15/08
Claims (3)
モニウムと共にメタノールを含む水溶液を電気分解して
水酸化第四アンモニウム水溶液を製造する方法におい
て、メタノール含量を１００ppm 以下とした上記水溶液
を電気分解に供することを特徴とする水酸化第四アンモ
ニウム水溶液の製造方法。1. A method for producing an aqueous quaternary ammonium hydroxide solution by electrolyzing an aqueous solution containing methanol together with tetramethylammonium hydrogen carbonate as a main component, wherein the aqueous solution having a methanol content of 100 ppm or less is subjected to electrolysis. A method for producing a quaternary ammonium hydroxide aqueous solution, comprising:
ノールの存在下で反応させて炭酸テトラメチルアンモニ
ウムメチルを含む反応混合物を得、この反応混合物に水
を加え、炭酸テトラメチルアンモニウムメチルを加水分
解して、主成分として炭酸水素テトラメチルアンモニウ
ムを含むと共にメタノール１００ppm 以下を含む水溶液
を得、これを水で希釈し、電気分解することを特徴とす
る水酸化第四アンモニウム水溶液の製造方法。2. A reaction mixture containing dimethyl carbonate and trimethylamine in the presence of methanol to obtain a reaction mixture containing tetramethylammonium methyl carbonate , and water is added to the reaction mixture to hydrolyze the tetramethylammonium methyl carbonate. A method for producing a quaternary ammonium hydroxide aqueous solution, comprising obtaining an aqueous solution containing tetramethylammonium hydrogen carbonate as a main component and containing 100 ppm or less of methanol, diluting the aqueous solution with water, and electrolyzing.
以下であることを特徴とする請求項１又は２記載の水酸
化第四アンモニウム水溶液の製造方法。3. The aqueous solution has a methanol content of 50 ppm.
The method for producing a quaternary ammonium hydroxide aqueous solution according to claim 1 or 2, wherein:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11197991A JP3260145B2 (en) | 1991-05-16 | 1991-05-16 | Method for producing quaternary ammonium hydroxide aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11197991A JP3260145B2 (en) | 1991-05-16 | 1991-05-16 | Method for producing quaternary ammonium hydroxide aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04341593A JPH04341593A (en) | 1992-11-27 |
| JP3260145B2 true JP3260145B2 (en) | 2002-02-25 |
Family
ID=14574915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11197991A Expired - Lifetime JP3260145B2 (en) | 1991-05-16 | 1991-05-16 | Method for producing quaternary ammonium hydroxide aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3260145B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2803856B1 (en) * | 2000-01-13 | 2002-07-05 | Atofina | SYNTHESIS OF TETRAMETHYLAMMONIUM HYDROXIDE |
| CN106350831A (en) * | 2016-08-26 | 2017-01-25 | 肯特催化材料股份有限公司 | Preparation method of molecular sieve template high-purity adamantyltrimethylammonium hydroxide water solution |
| CN106350832B (en) * | 2016-08-26 | 2018-04-10 | 肯特催化材料股份有限公司 | Molecular Sieves as Template agent high-purity hydrogen aoxidizes the preparation method of the hexamethonium C6 aqueous solution |
| CN106958028B (en) * | 2017-05-22 | 2019-05-07 | 江苏三吉利化工股份有限公司 | A kind of three Room, two membrane electrolysis prepares the device of high-purity tetrapropylammonium hydroxide |
| CN108911994A (en) * | 2018-06-11 | 2018-11-30 | 上海华银日用品有限公司 | A kind of environmental protection long chain alkyl ammonium salt solution and its continuous preparation method |
| CN113584508A (en) * | 2021-07-08 | 2021-11-02 | 枣阳市一鸣化工有限公司 | Treatment method of waste gas from silicone oil production |
-
1991
- 1991-05-16 JP JP11197991A patent/JP3260145B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04341593A (en) | 1992-11-27 |
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