JP3424687B2 - Method for producing quaternary ammonium hydroxide aqueous solution - Google Patents
Method for producing quaternary ammonium hydroxide aqueous solutionInfo
- Publication number
- JP3424687B2 JP3424687B2 JP12017393A JP12017393A JP3424687B2 JP 3424687 B2 JP3424687 B2 JP 3424687B2 JP 12017393 A JP12017393 A JP 12017393A JP 12017393 A JP12017393 A JP 12017393A JP 3424687 B2 JP3424687 B2 JP 3424687B2
- Authority
- JP
- Japan
- Prior art keywords
- quaternary ammonium
- aqueous solution
- tetramethylammonium
- weight
- acid salt
- 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 - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ＬＳＩやＬＣＤの製造
工程におけるポジ型レジストの現像液や基板等の洗浄液
等に使用される高純度な水酸化第四級アンモニウム水溶
液あるいは、ポリカーボネート樹脂用の重合触媒、ゼオ
ライト触媒の製造等に使用されている水酸化第四級アン
モニウム水溶液の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-purity quaternary ammonium hydroxide aqueous solution used for a positive resist developing solution, a substrate cleaning solution, or the like in a manufacturing process of LSI or LCD, or a polycarbonate resin. The present invention relates to a method for producing a quaternary ammonium hydroxide aqueous solution used for producing a polymerization catalyst, a zeolite catalyst and the like.
【０００２】[0002]
【従来の技術】水酸化第四級アンモニウム水溶液は、そ
の用途も広範囲に亘り、現在大量に生産されており、特
に近年、安価で高純度な水酸化第四級アンモニウム水溶
液が求められている。従来、水酸化第四級アンモニウム
の製造方法としては、次のような方法で行われている。2. Description of the Related Art Aqueous quaternary ammonium hydroxide solution has a wide range of uses and is currently produced in large quantities. Particularly, in recent years, inexpensive and highly pure aqueous quaternary ammonium hydroxide solution has been demanded. Conventionally, the following method has been used as a method for producing quaternary ammonium hydroxide.
【０００３】(1)トリアルキルアミンとハロゲン化アル
キルとを反応させ、第四級アンモニウムハロゲン化物を
合成し、この第四級アンモニウムハロゲン化物を電解し
て水酸化第四級アンモニウムを製造する方法。(2) トリ
アルキルアミンと有機カルボン酸エステルを反応させ、
第四級アンモニウム有機カルボン酸塩を合成し、この第
四級アンモニウム有機カルボン酸塩を電解して水酸化第
四級アンモニウムを製造する方法（特開昭６０−１００
６９０号）。(3) トリアルキルアミンと炭酸ジアルキル
エステルを反応させ、第四級アンモニウム無機酸塩を合
成し、この第四級アンモニウム無機酸塩を電解して、水
酸化第四級アンモニウムを製造する方法。（特開昭６１
−１７０５８８号）等がある。(1) A method for producing a quaternary ammonium hydroxide by reacting a trialkylamine with an alkyl halide to synthesize a quaternary ammonium halide, and electrolyzing the quaternary ammonium halide. (2) reacting a trialkylamine with an organic carboxylic acid ester,
Method for synthesizing quaternary ammonium organic carboxylic acid salt and electrolyzing this quaternary ammonium organic carboxylic acid salt to produce quaternary ammonium hydroxide (JP-A-60-100)
690). (3) A method for producing a quaternary ammonium hydroxide by reacting a trialkylamine with a carbonic acid dialkyl ester to synthesize a quaternary ammonium inorganic acid salt and electrolyzing the quaternary ammonium inorganic acid salt. (JP-A-61
-170588).
【０００４】上記（１）の方法では、電解工程で陽極中
に有害で腐食性のハロゲンイオン、ハロゲンガスが高濃
度で生成し、陽極自体、あるいは装置材質等を腐食する
などのトラブルが発生する。また、高純度の水酸化第四
級アンモニウム水溶液を製造する場合には、電解時にハ
ロゲンイオンが、イオン交換膜を通過して陰極側に移行
する、あるいは腐食による不純物の増加などの原因によ
り、純度低下を招く欠点を有している。In the above method (1), harmful and corrosive halogen ions and halogen gas are produced in a high concentration in the anode in the electrolysis process, and troubles such as corrosion of the anode itself or the material of the apparatus occur. . Further, in the case of producing a high-purity quaternary ammonium hydroxide aqueous solution, halogen ions during electrolysis move to the cathode side through the ion exchange membrane, or due to causes such as an increase in impurities due to corrosion, It has the drawback of causing a decrease.
【０００５】上記（２）の方法も電解工程で、腐食性の
有機酸イオンを生じ、陽極自体を腐食し、このギ酸イオ
ンを無害な炭酸ガスまで電解酸化するには、多大な電気
量を必要とする等の問題点を有している。また、高純度
の水酸化第四級アンモニウム水溶液を製造する場合には
電解時に、有機酸イオンがイオン交換膜を通過して、陰
極側に移行する、あるいは腐食による不純物の増加等の
原因により純度低下を招く欠点を有している。In the method (2), a large amount of electricity is required to generate corrosive organic acid ions in the electrolysis step, corrode the anode itself, and electrolytically oxidize the formate ions to harmless carbon dioxide gas. There are problems such as In the case of producing a high-purity quaternary ammonium hydroxide aqueous solution, during electrolysis, organic acid ions pass through the ion exchange membrane and migrate to the cathode side, or the purity increases due to the increase of impurities due to corrosion. It has the drawback of causing a decrease.
【０００６】上記（３）の製造方法は、原料として炭酸
ジアルキルエステルを使用するが、炭酸ジアルキルエス
テルが高価なため、安価な水酸化第四級アンモニウム水
溶液を製造するには好適でない。また、炭酸ジアルキル
エステルは、ホスゲンとアルコールから製造されるた
め、炭酸ジアルキルエステル中に、塩素化合物が混入す
る虞れがあり高純度の水酸化第四級アンモニウム水溶液
を製造する上で好ましくない。In the above-mentioned production method (3), a carbonic acid dialkyl ester is used as a raw material, but since the carbonic acid dialkyl ester is expensive, it is not suitable for manufacturing an inexpensive quaternary ammonium hydroxide aqueous solution. Further, since the carbonic acid dialkyl ester is produced from phosgene and alcohol, there is a possibility that a chlorine compound may be mixed in the carbonic acid dialkyl ester, which is not preferable in producing a high-purity quaternary ammonium hydroxide aqueous solution.
【０００７】[0007]
【発明が解決しようとする問題点】このように、従来の
製造方法には多くの問題点を有しており、いずれも充分
な製造方法とは言えず、安価で高純度な水酸化第四級ア
ンモニウム水溶液の製造方法が所望されている。本発明
は、上記のような従来方法の種々の問題点を解決し、安
価でかつ高純度な水酸化第四級アンモニウム水溶液の製
造方法を提供するものである。As described above, the conventional manufacturing methods have many problems, and none of them are sufficient manufacturing methods, and they are inexpensive and have high purity. A method for producing a quaternary ammonium aqueous solution is desired. The present invention solves various problems of the conventional methods as described above, and provides an inexpensive and highly pure method for producing a quaternary ammonium hydroxide aqueous solution.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記の従
来技術における種々の問題点を解決すべく鋭意検討を行
い、第四級アンモニウム有機酸塩を酸素または酸素を含
有するガスと反応させて第四級アンモニウム無機酸塩を
合成し、得られた第四級アンモニウム無機酸塩を電解に
より、水酸化第四級アンモニウムを得る新規な水酸化第
四級アンモニウムの製造法を見い出し、本発明を為すに
至った。DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies to solve various problems in the above-mentioned prior art, and reacted a quaternary ammonium organic acid salt with oxygen or a gas containing oxygen. By synthesizing a quaternary ammonium inorganic acid salt, and then electrolyzing the obtained quaternary ammonium inorganic acid salt to find a novel quaternary ammonium hydroxide production method, Invented.
【０００９】さらに、詳しくは第四級アンモニウム有機
酸塩の水溶液をパラジウム、白金、ルテニウム、ロジウ
ム、イリジウムの白金族触媒の存在下、１０〜２００℃
で酸素または酸素を含有するガスと反応させ、第四級ア
ンモニウム無機酸塩を合成し、得られた第四級アンモニ
ウム無機酸塩の水溶液をイオン交換膜を隔膜として用い
て電解槽を用いて電解する水酸化第四級アンモニウム水
溶液の製造法に関する。More specifically, an aqueous solution of a quaternary ammonium organic acid salt is heated at 10 to 200 ° C. in the presence of a platinum group catalyst of palladium, platinum, ruthenium, rhodium or iridium.
To react with oxygen or a gas containing oxygen to synthesize a quaternary ammonium inorganic acid salt, and the obtained aqueous solution of the quaternary ammonium inorganic acid salt is electrolyzed using an electrolytic cell using an ion exchange membrane as a diaphragm. To a method for producing a quaternary ammonium hydroxide aqueous solution.
【００１０】本発明における第四級アンモニウム有機酸
塩は、一般式〔Ｎ（Ｒ）4 〕+ ・Ｘ- で表される。（但
し、式中のＲは炭素数１〜３のアルキル基を表し、同一
であっても異なってもよい。Ｘはカルボキシル基を持つ
有機酸を示す。）[0010] quaternary ammonium organic acid salt in the present invention have the general formula [N (R) 4] + · X - is represented by. (However, R in the formula represents an alkyl group having 1 to 3 carbon atoms and may be the same or different. X represents an organic acid having a carboxyl group.)
【００１１】上記一般式で表される第四級アンモニウム
有機酸塩は、具体的にはテトラメチルアンモニウムギ酸
塩、テトラメチルアンモニウム酢酸塩、テトラメチルア
ンモニウムプロピオン酸塩、テトラメチルアンモニウム
シュウ酸塩、テトラメチルアンモニウムマロン酸塩、テ
トラメチルアンモニウムマレイン酸塩、テトラメチルア
ンモニウムコハク酸塩、テトラメチルアンモニウムフマ
ル酸塩、テトラメチルアンモニウムアクリル酸塩、テト
ラメチルアンモニウムメタアクリル酸塩、テトラメチル
アンモニウム安息香酸塩、テトラエチルアンモニウムギ
酸塩、テトラエチルアンモニウム酢酸塩、テトラエチル
アンモニウムプロピオン酸塩、テトラエチルアンモニウ
ムシュウ酸塩、トリメチルエチルアンモニウムギ酸塩、
トリメチルエチルアンモニウム酢酸塩、テトラプロピル
アンモニウムギ酸塩、テトラプロピルアンモニウム酢酸
塩等が挙げられる。これらの中でテトラメチルアンモニ
ウムギ酸塩、テトラエチルアンモニウムギ酸塩が好まし
い。なお、上記の第四級アンモニウム有機酸塩は、トリ
アルキルアミンと有機酸エステルより公知の方法により
容易に合成することができる。The quaternary ammonium organic acid salt represented by the above general formula is specifically tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium oxalate or tetramethylammonium oxalate. Methyl ammonium malonate, tetramethyl ammonium maleate, tetramethyl ammonium succinate, tetramethyl ammonium fumarate, tetramethyl ammonium acrylate, tetramethyl ammonium methacrylate, tetramethyl ammonium benzoate, tetraethyl Ammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium oxalate, trimethylethylammonium formate,
Examples include trimethylethylammonium acetate, tetrapropylammonium formate, tetrapropylammonium acetate, and the like. Of these, tetramethylammonium formate and tetraethylammonium formate are preferred. The quaternary ammonium organic acid salt can be easily synthesized from a trialkylamine and an organic acid ester by a known method.
【００１２】本発明に使用される白金族触媒は、パラジ
ウム、白金、ルテニウム、ロジウム、イリジウム金属を
活性炭、炭素繊維、活性炭素繊維等の炭素材、シリカ、
アルミナ、シリカアルミナ、ゼオライト等の担体に担持
した触媒が使用される。これらの触媒の中で、パラジウ
ムを炭素材に担持した触媒が好ましい。The platinum group catalyst used in the present invention includes palladium, platinum, ruthenium, rhodium, iridium metal, activated carbon, carbon material such as activated carbon fiber, silica, silica,
A catalyst supported on a carrier such as alumina, silica alumina, or zeolite is used. Among these catalysts, a catalyst in which palladium is supported on a carbon material is preferable.
【００１３】本発明の白金族触媒は、パラジウム、白
金、ルテニウム、ロジウム、イリジウム金属を上記担体
に対して０．０１〜２０重量％、好ましくは０．０５〜
１０重量％担持した触媒が好ましい。The platinum group catalyst of the present invention contains palladium, platinum, ruthenium, rhodium or iridium metal in an amount of 0.01 to 20% by weight, preferably 0.05 to 20% by weight, based on the carrier.
A catalyst loaded with 10% by weight is preferred.
【００１４】本発明における第四級アンモニウム有機酸
塩と酸素または酸素を含有するガスとの反応は、上記白
金族触媒の存在下で反応温度１０〜２００℃、好ましく
は２０〜１５０℃の範囲で行われる。なお、本発明にお
ける第四級アンモニウム有機酸塩と酸素の反応は、常圧
または加圧下いずれでも実施し得る。また反応は回分
式、半回分式あるいは連続式の何れの方法でも実施でき
る。The reaction of the quaternary ammonium organic acid salt with oxygen or a gas containing oxygen in the present invention is carried out in the presence of the platinum group catalyst at a reaction temperature of 10 to 200 ° C., preferably 20 to 150 ° C. Done. The reaction of the quaternary ammonium organic acid salt with oxygen in the present invention can be carried out under either normal pressure or increased pressure. The reaction can be carried out by any of batch method, semi-batch method and continuous method.
【００１５】さらに本発明における第四級アンモニウム
有機酸塩と酸素のモル比は０．５以上であり、使用され
る第四級アンモニウム有機酸塩の種類、触媒の種類、反
応条件を勘案して適宜選択されるが、一般的には０．５
〜１００の範囲、好ましくは０．５〜５０の範囲で行わ
れる。Further, the molar ratio of the quaternary ammonium organic acid salt to oxygen in the present invention is 0.5 or more, and the kind of the quaternary ammonium organic acid salt used, the kind of the catalyst, and the reaction conditions are taken into consideration. It is appropriately selected, but generally 0.5
To 100, preferably 0.5 to 50.
【００１６】本発明における第四級アンモニウム有機酸
塩と酸素または酸素含有ガスとの反応で得られた第四級
アンモニウム無機酸塩の電解は、通常陽イオン交換膜で
陽極と陰極とに区画された電解槽が使用されるが、この
他に二枚以上の陽イオン交換膜によって陽極室、陰極室
および１室以上の中間室に区画された電解槽を使用する
ことができる。The electrolysis of the quaternary ammonium inorganic acid salt obtained by the reaction of the quaternary ammonium organic acid salt with oxygen or an oxygen-containing gas in the present invention is usually divided into an anode and a cathode by a cation exchange membrane. In addition to this, an electrolytic cell divided into an anode chamber, a cathode chamber and one or more intermediate chambers by two or more cation exchange membranes can be used.
【００１７】本発明に使用される陽イオン交換膜として
は、スルフォン基、カルボン酸基等の陽イオン交換基を
有する耐腐食性のあるフッ素樹脂系のものが好適に使用
されるが、これ以外に上記の交換基を有するスチレン−
ジビニルベンゼン共重合体系のものも使用し得る。As the cation exchange membrane used in the present invention, a corrosion resistant fluororesin-based one having a cation exchange group such as a sulfone group or a carboxylic acid group is preferably used. Styrene having the above-mentioned exchange group
Divinylbenzene copolymer type may also be used.
【００１８】本発明の電解槽に使用される陽極として
は、高純度な炭素電極、白金、イリジウム等の白金族酸
化物で被覆されたチタン電極等この種の電解に使用され
る電極が使用される。また、本発明陰極としては、ステ
ンレス鋼、ニッケル等のこの種の電解において使用され
る電極が使用される。これらの陽極、陰極は、板状、網
状、多孔板状等の何れの形状でも使用し得る。As the anode used in the electrolytic cell of the present invention, an electrode used for this type of electrolysis such as a high-purity carbon electrode or a titanium electrode coated with a platinum group oxide such as platinum or iridium is used. It As the cathode of the present invention, an electrode used in this type of electrolysis, such as stainless steel or nickel, is used. These anodes and cathodes may be used in any shape such as a plate shape, a net shape and a perforated plate shape.
【００１９】本発明において、電解槽における電解は直
流電圧を印加することによって行われるが、その電流密
度は１〜 100Ａ／ｄｍ2 、好ましくは、３〜５０Ａ／ｄ
ｍ2である。また電解時の温度は、１０〜５０℃の範囲
で行うことが好ましい。本発明における電解は回分式、
連続式何れでも行うことができ、この際、陽極室に供給
する原料の第四級アンモニウム無機酸塩の濃度は、１〜
６０重量％好ましくは３〜４０重量％に設定される。ま
た、陰極室には、通常水が供給されるが、運転開始時に
は、水単独では電気伝導度が低く、電解が起こり難いの
で、目的物である水酸化第四級アンモニウムを少量、例
えば０．０１〜５重量％添加した液を用いることが望ま
しい。また、電解中は窒素、アルゴンなどの不活性ガス
の雰囲気で行うことが望ましい。In the present invention, electrolysis in the electrolytic cell is carried out by applying a DC voltage, and the current density is 1 to 100 A / dm 2 , preferably 3 to 50 A / d.
m 2 . The temperature during electrolysis is preferably in the range of 10 to 50 ° C. The electrolysis in the present invention is a batch type,
It can be carried out by any of continuous methods. At this time, the concentration of the quaternary ammonium inorganic acid salt as a raw material supplied to the anode chamber is 1 to
It is set to 60% by weight, preferably 3 to 40% by weight. Further, water is usually supplied to the cathode chamber, but at the start of the operation, water alone has a low electric conductivity and electrolysis is difficult to occur. It is desirable to use a solution added with 01 to 5% by weight. Further, it is desirable to perform the electrolysis in an atmosphere of an inert gas such as nitrogen or argon.
【００２０】以下に本発明の実施例を示す。
実施例１
粒径１〜２ｍｍの活性炭に０．５重量％のパラジウムを
担持した触媒を、内径４０ｍｍの反応器に１リットル充
填した。８０℃に加熱し、酸素ガスを２００リットル／
時間の流速で供給し、反応器にテトラメチルアンモニウ
ムギ酸塩２０．６重量％を含有する水溶液を常圧下３０
０ｇ／時間の流速で供給した。反応後のテトラメチルア
ンモニウム無機酸塩の濃度は２２．９重量％でテトラメ
チルアンモニウムギ酸塩は０．０８１重量％であった。Examples of the present invention will be shown below. Example 1 A catalyst having 0.5% by weight of palladium supported on activated carbon having a particle diameter of 1 to 2 mm was charged in a reactor having an inner diameter of 40 mm in an amount of 1 liter. Heat to 80 ° C and add 200 liters of oxygen gas /
An aqueous solution containing 20.6% by weight of tetramethylammonium formate is fed to the reactor at a flow rate of 30 hours under normal pressure.
It was supplied at a flow rate of 0 g / hour. After the reaction, the concentration of the tetramethylammonium inorganic acid salt was 22.9% by weight, and the concentration of the tetramethylammonium formate salt was 0.081% by weight.
【００２１】次に、陽イオン交換膜としてＮａｆｉｏｎ
３２４（デュポン社製フッ素系陽イオン交換膜）を使用
し電解槽を陽極室と陰極室に区画し、陽極には白金を被
覆したチタン電極を、陰極にはニッケルを電極とした装
置を使用し、陽極室に上記のテトラメチルアンモニウム
無機酸塩の２２．９重量％水溶液を循環した。陰極室に
は、０．５重量％のテトラメチルアンモニウム水酸化物
水溶液を循環し、１０Ａ／ｄｍ2 の直流電流を印加し、
温度３５℃にて電解を行った。電解電圧は５〜６Ｖ、平
均電流効率は８８％で、陰極室に１７．０重量％のテト
ラメチルアンモニウム水酸化物水溶液が得られた。な
お、電解後の陰極室中のテトラメチルアンモニウムギ酸
塩の濃度は、０．００２重量％であった。Next, as a cation exchange membrane, Nafion is used.
324 (DuPont fluorinated cation exchange membrane) was used to divide the electrolytic cell into an anode chamber and a cathode chamber, a titanium electrode coated with platinum was used for the anode, and a nickel electrode was used for the cathode. A 22.9% by weight aqueous solution of the above tetramethylammonium inorganic acid salt was circulated in the anode chamber. In the cathode chamber, 0.5 wt% tetramethylammonium hydroxide aqueous solution was circulated, and a direct current of 10 A / dm 2 was applied,
Electrolysis was performed at a temperature of 35 ° C. The electrolysis voltage was 5 to 6 V, the average current efficiency was 88%, and a 17.0 wt% tetramethylammonium hydroxide aqueous solution was obtained in the cathode chamber. The concentration of tetramethylammonium formate in the cathode chamber after electrolysis was 0.002% by weight.
【００２２】実施例２
実施例１で使用した同様の反応器を６０℃に加熱し、空
気を流速４６０リットル／時間で供給しながらトラメチ
ルアンモニウムギ酸塩を１０．１重量％を含有する水溶
液を常圧下４００ｇ／時間の流速で供給した。 反応後
のテトラメチルアンモニウム無機酸塩の濃度は、１１．
１重量％で、テトラメチルアンモニウムギ酸塩は、０．
０３重量％であった。Example 2 A reactor similar to that used in Example 1 was heated to 60 ° C., and an aqueous solution containing 10.1% by weight of tramethylammonium formate was supplied while air was supplied at a flow rate of 460 liters / hour. It was supplied at a flow rate of 400 g / hour under normal pressure. The concentration of the tetramethylammonium inorganic acid salt after the reaction was 11.
At 1% by weight, tetramethylammonium formate is 0.1%.
It was 03% by weight.
【００２３】次に陽極としてイリジウム酸化物を被覆し
たチタン電極とした以外は、実施例１と同様の電解槽を
使用し、陽極室に上記のテトラメチルアンモニウム無機
酸塩の１１．１重量％水溶液を循環した。陰極室に０．
３重量％のテトラメチルアンモニウム水酸化物水溶液を
循環し、１５Ａ／ｄｍ2 の直流電流を印加し、温度４０
℃にて電解を行った。電解電圧は７〜９Ｖであり、平均
電流効率は８４％で陰極室に２１．９重量％のテトラメ
チルアンモニウム水酸化物水溶液が得られた。なお、電
解後の陰極室中のテトラメチルアンモニウムギ酸塩の濃
度は０．００２重量％であったNext, the same electrolytic cell as in Example 1 was used, except that a titanium electrode coated with iridium oxide was used as the anode, and an 11.1 wt% aqueous solution of the above tetramethylammonium inorganic acid salt was used in the anode chamber. Circulated. 0.
A 3% by weight tetramethylammonium hydroxide aqueous solution was circulated, a direct current of 15 A / dm 2 was applied, and a temperature of 40
Electrolysis was performed at ° C. The electrolysis voltage was 7 to 9 V, the average current efficiency was 84%, and 21.9% by weight of a tetramethylammonium hydroxide aqueous solution was obtained in the cathode chamber. The concentration of tetramethylammonium formate in the cathode chamber after electrolysis was 0.002% by weight.
【００２４】実施例３
粒径１〜２ｍｍの活性炭に０．５重量％の白金を担持し
た触媒を実施例１に使用したと同様の反応器に１リット
ル充填した。５０℃に加熱し、酸素を５００リットル／
時間の流速で供給する反応器に、テトラメチルアンモニ
ウムギ酸塩９．５重量％、を含有する水溶液を常圧下で
２００ｇ／時間の流速で供給した。反応後のテトラメチ
ルアンモニウム無機酸塩の濃度は１０．２重量％であ
り、テトラメチルアンモニウムギ酸塩は０．００５重量
％であった。Example 3 The same reactor as used in Example 1 was charged with 1 liter of a catalyst prepared by loading 0.5% by weight of platinum on activated carbon having a particle diameter of 1 to 2 mm. Heat to 50 ° C and add 500 liters of oxygen
An aqueous solution containing tetramethylammonium formate 9.5% by weight was fed at a flow rate of 200 g / hour under normal pressure to the reactor fed at a flow rate of time. After the reaction, the concentration of the tetramethylammonium inorganic acid salt was 10.2% by weight, and the content of the tetramethylammonium formate was 0.005% by weight.
【００２５】実施例２で使用した同様の電解槽を使用
し、陽極室に上記のテトラメチルアンモニウム無機酸塩
の１１．１重量％水溶液を循環した。陰極室に０．５重
量％のテトラメチルアンモニウム水酸化物水溶液を循環
し２０Ａ／ｄｍ2 の直流電流を印加し、温度４０℃にて
電解を行った。電解電圧は８〜１２Ｖであり、平均電流
効率は８１％で陰極室に８．２重量％のテトラメチルア
ンモニウム水酸化物水溶液が得られた。なお、電解後の
陰極室中のテトラメチルアンモニウムギ酸塩の濃度は、
０．０００１重量％以下であった。Using the same electrolytic cell used in Example 2, an 11.1 wt% aqueous solution of the above tetramethylammonium inorganic acid salt was circulated in the anode chamber. 0.5 wt% tetramethylammonium hydroxide aqueous solution was circulated in the cathode chamber, a direct current of 20 A / dm 2 was applied, and electrolysis was performed at a temperature of 40 ° C. The electrolysis voltage was 8 to 12 V, the average current efficiency was 81%, and 8.2% by weight of a tetramethylammonium hydroxide aqueous solution was obtained in the cathode chamber. The concentration of tetramethylammonium formate in the cathode chamber after electrolysis is
It was 0.0001% by weight or less.
【００２６】実施例４
実施例１に使用したと同様の触媒、反応器を用い、反応
圧力を８ｋｇ／ｃｍ2の条件とした以外は実施例１と同
一の条件で行った。反応後のテトラメチルアンモニウム
無機酸塩の濃度は、２３．０重量％でテトラメチルアン
モニウムギ酸塩は０．０１重量％であった。Example 4 Example 4 was carried out under the same conditions as Example 1 except that the same catalyst and reactor as those used in Example 1 were used and the reaction pressure was set to 8 kg / cm 2 . After the reaction, the concentration of the tetramethylammonium inorganic acid salt was 23.0% by weight, and the concentration of the tetramethylammonium formate salt was 0.01% by weight.
【００２７】実施例２で使用した同一の電解槽を使用
し、陽極室には上記のテトラメチルアンモニウム無機酸
塩の２３．０重量％水溶液を循環した。陰極室には、
０．５重量％のテトラメチルアンモニウム水酸化物水溶
液を循環し、１０Ａ／ｄｍ2 の直流電流を印加し、温度
３５℃で電解を行った。電解電圧５〜６Ｖ、平均電流効
率は８９％で、陰極室には１７．９重量％のテトラメチ
ルアンモニウム水酸化物水溶液が得られた。なお、電解
後の陰極室中のテトラメチルアンモニウムギ酸塩の濃度
は、０．０００１重量％以下であった。The same electrolytic cell used in Example 2 was used, and a 23.0 wt% aqueous solution of the above tetramethylammonium inorganic acid salt was circulated in the anode chamber. In the cathode chamber,
Electrolysis was carried out at a temperature of 35 ° C. by circulating a 0.5 wt% tetramethylammonium hydroxide aqueous solution and applying a direct current of 10 A / dm 2 . The electrolysis voltage was 5 to 6 V, the average current efficiency was 89%, and a 17.9 wt% tetramethylammonium hydroxide aqueous solution was obtained in the cathode chamber. The concentration of tetramethylammonium formate in the cathode chamber after electrolysis was 0.0001% by weight or less.
【００２８】実施例５
実施例１で使用したと同様の反応器を５０℃に加熱し、
酸素ガスを２００リットル／時間の流速で供給しなが
ら、テトラエチルアンモニウムギ酸塩を１４．０重量％
を含有する水溶液を常圧下で２００ｇ／時間の流速で供
給した。反応後のテトラエチルアンモニウム無機酸塩の
濃度は、１４．７重量％でテトラエチルアンモニウムギ
酸塩は０．０１重量％であった。Example 5 A reactor similar to that used in Example 1 was heated to 50 ° C,
While supplying oxygen gas at a flow rate of 200 liters / hour, 14.0% by weight of tetraethylammonium formate was added.
Was supplied at a flow rate of 200 g / hour under normal pressure. After the reaction, the concentration of the tetraethylammonium inorganic acid salt was 14.7% by weight, and the concentration of the tetraethylammonium formate was 0.01% by weight.
【００２９】次に実施例２で使用した同様の電解槽を使
用し、陽極室には上記のテトラエチルアンモニウム無機
酸塩の１４．７重量％水溶液を循環し、陰極室には、
０．５重量％のテトラエチルアンモニウム水酸化物水溶
液を循環し、２０Ａ／ｄｍ2 の直流電流を印加し、温度
４０℃で電解を行った。電解電圧１０〜１４Ｖであり、
平均電流効率は７５％で、陰極室には１２．８重量％の
テトラエチルアンモニウム水酸化物水溶液が得られた。
なお、電解後の陰極室中のテトラエチルアンモニウムギ
酸塩の濃度は、０．００８重量％以下であった。Next, using the same electrolytic cell as used in Example 2, a 14.7 wt% aqueous solution of the above tetraethylammonium inorganic acid salt was circulated in the anode chamber, and the cathode chamber was
A 0.5 wt% tetraethylammonium hydroxide aqueous solution was circulated, a direct current of 20 A / dm 2 was applied, and electrolysis was performed at a temperature of 40 ° C. Electrolysis voltage is 10-14V,
The average current efficiency was 75%, and a 12.8 wt% tetraethylammonium hydroxide aqueous solution was obtained in the cathode chamber.
The concentration of tetraethylammonium formate in the cathode chamber after electrolysis was 0.008% by weight or less.
【００３０】[0030]
【発明の効果】本発明によれば、ハロゲンイオンや有機
酸イオンの混入のない高純度の水酸化第四級アンモニウ
ム水溶液を効率よく安価に製造することができる。According to the present invention, a high-purity quaternary ammonium hydroxide aqueous solution containing no halogen ions or organic acid ions can be efficiently and inexpensively produced.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−70080（ＪＰ，Ａ) 特開 昭64−87797（ＪＰ，Ａ) 特開 昭63−134684（ＪＰ，Ａ) 特開 昭63−24080（ＪＰ，Ａ) 特開 昭61−170588（ＪＰ，Ａ) 特開 昭60−131986（ＪＰ，Ａ) 特開 昭60−100690（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 209/68 B01J 23/40 C07C 211/63 C25B 3/00 C07B 61/00 300 ─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-2-70080 (JP, A) JP-A 64-87797 (JP, A) JP-A 63-134684 (JP, A) JP-A 63- 24080 (JP, A) JP 61-170588 (JP, A) JP 60-131986 (JP, A) JP 60-100690 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C07C 209/68 B01J 23/40 C07C 211/63 C25B 3/00 C07B 61/00 300
Claims (3)
触媒の存在下に、酸素または酸素を含有するガスと反応
させてテトラメチルアンモニウム重炭酸塩を合成し、こ
のテトラメチルアンモニウム重炭酸塩を電解することを
特徴とする水酸化第四級アンモニウム水溶液の製造方
法。The method according to claim 1] tetramethylammonium formate, in the presence of a platinum catalyst, is reacted with an oxygen-containing gas or oxygen to synthesize tetramethylammonium bicarbonate, electrolyzing the tetramethylammonium bicarbonate A method for producing an aqueous quaternary ammonium hydroxide solution, which comprises:
触媒の存在下に、酸素または酸素を含有するガスと反応
させてテトラエチルアンモニウム重炭酸塩を合成し、こ
のテトラエチルアンモニウム重炭酸塩を電解することを
特徴とする水酸化第四級アンモニウム水溶液の製造方
法。2. A method tetraethylammonium formate, characterized in the presence of a platinum catalyst, it is reacted with an oxygen-containing gas or oxygen to synthesize tetraethylammonium bicarbonate, electrolyzing the tetraethylammonium bicarbonate And a method for producing a quaternary ammonium hydroxide aqueous solution.
ム、ロジウム、イリジウムから選ばれた少なくとも一種
である請求項１又は２記載の水酸化第四級アンモニウム
水溶液の製造方法。3. A platinum catalyst, palladium, platinum, ruthenium, rhodium, at least one type of claim 1 or 2 quaternary ammonium aqueous method for producing hydroxide according selected from iridium.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12017393A JP3424687B2 (en) | 1993-05-21 | 1993-05-21 | Method for producing quaternary ammonium hydroxide aqueous solution |
| US08/168,049 US5393386A (en) | 1992-12-28 | 1993-12-15 | Method for preparing aqueous quaternary ammonium hydroxide solution |
| EP93120484A EP0608545B1 (en) | 1992-12-28 | 1993-12-18 | Method for preparing aqueous quaternary ammonium hydroxide solution |
| DE69309885T DE69309885T2 (en) | 1992-12-28 | 1993-12-18 | Process for the preparation of aqueous solutions of quaternary ammonium hydroxides |
| KR1019930029846A KR100242979B1 (en) | 1992-12-28 | 1993-12-27 | The method for preparing aqueous quaternary ammonium hydroxide solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12017393A JP3424687B2 (en) | 1993-05-21 | 1993-05-21 | Method for producing quaternary ammonium hydroxide aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06329602A JPH06329602A (en) | 1994-11-29 |
| JP3424687B2 true JP3424687B2 (en) | 2003-07-07 |
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ID=14779734
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|---|---|---|---|
| JP12017393A Expired - Fee Related JP3424687B2 (en) | 1992-12-28 | 1993-05-21 | Method for producing quaternary ammonium hydroxide aqueous solution |
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| Country | Link |
|---|---|
| JP (1) | JP3424687B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0860425B1 (en) * | 1996-07-23 | 2000-11-02 | Tokuyama Corporation | Process for the preparation of aqueous solutions of tetraalkylammonium hydroxides |
| CN110225667B (en) * | 2013-09-11 | 2023-01-10 | 花王株式会社 | Detergent composition for resin mask layer and method for manufacturing circuit board |
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- 1993-05-21 JP JP12017393A patent/JP3424687B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH06329602A (en) | 1994-11-29 |
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