WO2011036942A1

WO2011036942A1 - Process for production of tetraalkylammonium hydroxide

Info

Publication number: WO2011036942A1
Application number: PCT/JP2010/062700
Authority: WO
Inventors: 誠佐藤; 淳渡邉; 昭子村田
Original assignee: 株式会社トクヤマ
Priority date: 2009-09-24
Filing date: 2010-07-28
Publication date: 2011-03-31
Also published as: CN102510853A; KR20120070564A; JPWO2011036942A1

Abstract

Disclosed is a process for producing an aqueous tetraalkylammonium hydroxide (TAA-OH) solution by bringing an OH-type anion exchange resin produced by regenerating a Cl-type ion exchange resin into contact with a raw material solution comprising 1 to 20 mass% of an aqueous tetraalkylammonium chloride (TAA-Cl) solution. In the process, an OH-type anion exchange resin that is produced by a generally employed regeneration technique and has a relatively large Cl residue content is brought into contact with the raw material solution to produce a primary reaction solution comprising an aqueous TAA-OH solution having a TAA-Cl concentration of 0.01 to 1 mass%, and the primary reaction solution is brought into contact with an OH-type anion exchange resin having an extremely low Cl residue content to produce an aqueous TAA-OH solution having a TAA-Cl concentration of less than 0.01 mass%. In this manner, a process for producing a TAA-OH can be provided, which is applicable to a method for collecting an aqueous TAA-OH solution having a low impurity content safely and with high efficiency from an aqueous liquid waste containing a TAA-OH without the need of carrying out electrophoresis or electrolysis.

Description

Method for producing tetraalkylammonium hydroxide

The present invention relates to a method for producing tetraalkylammonium hydroxide from a tetraalkylammonium halide. More specifically, tetraalkylammonium hydroxide can be suitably used in a method for recovering tetraalkylammonium hydroxide in a reusable form from waste liquid obtained after using a developer comprising an aqueous tetraalkylammonium hydroxide solution. It relates to a manufacturing method.

Tetraalkylammonium hydroxide (hereinafter sometimes abbreviated as “TAA-OH”) aqueous solution is used for semiconductor substrate cleaning, etching, photoresist development, etc. in the manufacture of integrated circuits and large-scale integrated circuits. It is used as a treatment agent.

Conventionally, the waste liquid of such a treatment agent is incinerated after concentration of organic residues such as TAA-OH and photoresist components by removing water by an evaporation method or a reverse osmosis membrane method, or activated sludge treatment (biological treatment) The mainstream was the method of releasing it into rivers after being decomposed. However, in recent years, considering environmental considerations, it has been studied to recover TAA-OH from waste liquid and reuse it.

As a method for recycling the waste liquid containing TAA-OH, the following method is known.
(A) A method of recovering a TAA-OH aqueous solution by neutralizing the concentrated waste liquid to remove the photoresist component and then performing electrodialysis or electrolysis (see Patent Documents 1 to 3).
(B) The waste liquid is brought into contact with a cation exchange resin to adsorb a tetraalkylammonium cation (hereinafter also referred to as “TAA cation”) to the cation exchange resin, and then the cation exchange resin is dissolved in an aqueous inorganic hydroxide solution. The TAA cation is desorbed as TAA-OH by treating with, and a TAA-OH aqueous solution is recovered (see Patent Document 4).
(C) After contacting the waste liquid with a cation exchange resin to adsorb the TAA cation to the cation exchange resin, the cation exchange resin is treated with hydrochloric acid to convert the TAA cation to a tetraalkylammonium chloride (hereinafter referred to as “TAA-Cl”). And is recovered as a TAA-Cl aqueous solution, and perchloric acid is added to the resulting aqueous solution to form a tetraalkylammonium perchlorate (hereinafter referred to as “TAA perchlorate”). The obtained TAA perchlorate is purified by crystallization, dissolved again in water, and the obtained aqueous solution is contacted with an OH-type anion exchange resin to obtain a TAA-OH aqueous solution. A method of collecting (see Patent Document 5).

Japanese Patent Laid-Open No. 04-228587 Japanese Patent Laid-Open No. 05-106074 Japanese Patent No. 3216998 Japanese Patent No. 4142432 JP 2003-340449 A

The method shown in (a) has a merit that high-purity TAA-OH can be obtained, but has a demerit that a special dedicated facility is required to perform electrodialysis or electrolysis. For example, waste liquid generated in a factory or the like where such equipment cannot be installed from the viewpoint of installation cost and installation space must be collected and transported to a recycling facility having such equipment. Further, when treating a waste liquid having a low TAA-OH concentration, it has been necessary to concentrate the TAA-OH waste liquid to such a concentration that enables efficient electrodialysis or electrolysis.

Although the method shown in (b) above does not require special dedicated equipment, if organic impurities such as a photoresist component are not highly removed before the adsorption treatment, these organic impurities are easily dissolved in an alkaline aqueous solution. Therefore, when the desorption treatment is performed with the inorganic hydroxide aqueous solution, there is a problem that the organic impurities physically adsorbed on the ion exchange resin during the adsorption treatment are simultaneously desorbed and mixed into the recovered TAA-OH aqueous solution. .

In addition to the advantage that no special dedicated equipment is required, the method shown in (c) differs from the method (b) in that the TAA cation is desorbed in an acidic aqueous solution, so that the physically adsorbed organic There is also a merit that mixing into the recovered liquid accompanying the elution of impurities can be avoided. However, in this method, it is necessary to convert TAA-OH once to TAA perchlorate, and then to separate and purify it, and TAA perchlorate explodes due to contact with and impact with organic substances during handling. Not only is there a danger, but the purified perchlorate has to be redissolved in water, and there is a problem that the operation becomes complicated.

Therefore, the present invention can recover a TAA-OH aqueous solution containing a small amount of impurities safely and efficiently from an aqueous waste solution containing TAA-OH without electrodialysis or electrolysis. It aims at providing the manufacturing method of.

If the TAA-Cl aqueous solution obtained by desorbing the TAA cation from the cation exchange resin in the method (c) can be converted into a TAA-OH aqueous solution by a simpler method, We thought that we were able to achieve our objectives and conducted intensive studies.

As a result, the knowledge that the intended purpose can be achieved by exchanging Cl ions (anions) of TAA-Cl with OH ions (anions) using an OH type anion exchange resin, and TAA- When an OH aqueous solution is obtained, there is a new problem that is difficult to make the concentration of Cl ions (anions) contained in the obtained aqueous solution 100 ppm or less, which is not found in the method (c). I got the knowledge. The method can also be applied to TAA-halogens obtained by desorbing TAA cations from cation exchange resins using hydrogen halide, and it has been found that a TAA-OH aqueous solution can be obtained. It was.

As a result of further investigations to solve this new problem, 1) OH type anion exchange resin is usually obtained by treating Cl type anion exchange resin with an inorganic hydroxide aqueous solution. Even after this treatment, Cl ions remain as counter ions of the anion exchange group, and the amount of the remaining Cl ions is greatly related to the above problem, and 2) the concentration of Cl ions (anions) to be mixed is determined. In order to lower the concentration, the aqueous solution is brought into contact with an OH-type anion exchange resin with a very small amount of residual Cl in a state where the concentration of TAA-halogen in the aqueous solution is lowered to 0.01 to 1% by mass by ion exchange. Was found to be effective, and the present invention was completed as follows.

That is, the present invention is as shown in the following [1] to [7].
[1] (A) Contacting a Cl-type anion exchange resin having Cl ions as a counter ion of an anion exchange group with an aqueous inorganic hydroxide solution, the counter ion of the anion exchange group is changed from Cl ion to OH ion. "Anion exchange resin treatment step" for preparing an OH type anion exchange resin having OH ions as counter ions of anion exchange groups by exchange, and (B) the OH type anion exchange prepared in the above step The resin is brought into contact with a raw material solution comprising a tetraalkylammonium halide aqueous solution having a tetraalkylammonium halide concentration of 1 to 20% by mass, and the tetraalkylammonium halide is converted into a tetraalkylammonium hydroxide by an anion exchange reaction. "Reaction process" to convert,
A process for producing a tetraalkylammonium hydroxide comprising
In the anion exchange resin treatment step (A), after contacting the Cl-type anion exchange resin with an inorganic hydroxide aqueous solution, the OH-type anion obtained after sufficiently washing with water until no Cl ions can be detected. 100 parts by volume of ion exchange resin is packed in a packed column, and is contained in the final 200 volume parts of effluent that flows out when 500 parts by volume of 0.5N (N) sodium hydroxide aqueous solution is passed through the packed column. Preparing a high purity OH type anion exchange resin having a Cl ion elution amount defined as a Cl ion concentration of less than 100 ppm and a normal purity OH type anion exchange resin having a Cl ion elution amount of 100 ppm or more,
The reaction step (B)
(B-1) By bringing the raw material solution into contact with the normal purity OH type anion exchange resin, or the normal purity OH type anion exchange resin and the high purity OH type anion exchange resin, A primary reaction step of obtaining a primary reaction solution comprising a tetraalkylammonium hydroxide aqueous solution containing tetraalkylammonium bromide at a concentration of 0.01 to 1% by mass; and
(B-2) The primary reaction solution and the high-purity OH-type anion exchange resin are brought into contact with each other to form a tetraalkylammonium hydroxide aqueous solution having a tetraalkylammonium halide concentration of less than 0.01% by mass. A secondary reaction step for obtaining a secondary reaction solution;
A process for producing a tetraalkylammonium hydroxide, comprising:

[2] The method according to [1], wherein the high-purity OH type anion exchange resin used in the step (B-2) is a strongly basic anion exchange resin.

[3] The reaction step (B) is performed by supplying the raw material solution to the ion exchange column filled with the OH type anion exchange resin prepared in the anion exchange resin treatment step (A). The high-purity OH-type anion exchange resin is disposed in the most downstream region of the ion exchange column, and the primary reaction is performed in a region upstream of the most downstream portion in the ion exchange column. Performing the step (B-1) and performing the secondary reaction step (B-2) in the most downstream region.

[4] A plurality of the ion exchange towers are prepared, these ion exchange towers are connected in series by piping, and the high-purity OH type anion exchange resin is arranged in the whole or the most downstream part of the most downstream ion exchange tower. The method according to [3] above.

[5] An ion exchange column filled with a Cl-type anion exchange resin is prepared, and an aqueous solution of inorganic hydroxide is circulated in the ion exchange column from the downstream side to the upstream side in the reaction step (B). [3] or [4], wherein the anion exchange resin treatment step (A) is performed and the high-purity OH type anion exchange resin is disposed in the most downstream region of the ion exchange column. The method described in 1.

[6] A production cycle comprising the anion exchange resin treatment step (A) and the subsequent reaction step (B) is repeated, and the step (A in the n-th production cycle (where n is a natural number)) ) And step (B) are (A ⁿ ) and (B ⁿ ), respectively, in each anion exchange resin treatment step (A ⁿ ) after the second production cycle, the immediately preceding reaction step (B The method according to [5] above, wherein the OH-type anion exchange resin converted into a halogen-type anion exchange resin by an anion exchange reaction in ^n-1 ) is regenerated into an OH-type anion exchange resin.

[7] (P-1) By bringing a tetraalkylammonium hydroxide aqueous solution in which organic impurities are dissolved into contact with a cation exchange resin, the cation exchange resin is contacted with a tetraalkyl as a counter ion of the cation exchange group. An adsorption step for retaining ammonium cations, and
(P-2) A deionization in which a cation exchange resin having a tetraalkylammonium cation as a counter ion obtained in the adsorption step is contacted with a hydrogen halide to desorb the tetraalkylammonium cation as a tetraalkylammonium halide. Separation process,
The method according to any one of [1] to [6], further comprising a raw material solution preparation step (P) comprising:

According to the method of the present invention, from a TAA-halogen aqueous solution, a low-cost and high-efficiency Cl ion concentration (or TAA-Cl concentration) or a TAA-OH aqueous solution having a very low halogen ion concentration (or TAA-halogen concentration). Can be manufactured. For example, a TAA-OH aqueous solution having a very low Cl ion concentration of, for example, 100 ppm or less, preferably 50 ppm or less, and most preferably 10 ppm or less can be easily obtained by a simple operation without special purification. The halogen ion concentration can be preferably 100 ppm or less, more preferably 50 ppm or less.

In the method of the present invention, it is necessary to bring the TAA-halogen aqueous solution into contact with the high-purity OH type anion exchange resin in order to obtain the above-described effects. Since it suffices to carry out only at the final stage where anion exchange has advanced, the amount of high-purity OH type anion exchange resin to be used can be reduced. In order to obtain a high-purity OH-type anion exchange resin from a Cl-type anion exchange resin, it is necessary to use a large amount of an aqueous inorganic hydroxide solution. Can be reduced.

In the method of the present invention, in the reaction step (B), the OH type anion exchange resin is changed to a halogen type anion exchange resin by an anion exchange reaction, but the anion exchange resin treatment step (A) is thus performed. Since it can also function as a regeneration process for the changed halogen-type anion exchange resin, it is possible to repeat the production cycle comprising the anion exchange resin treatment process (A) and the subsequent reaction process (B). is there.

In the method of the present invention, an aqueous TAA-halogen (eg, TAA-Cl) aqueous solution obtained by treating an aqueous waste solution containing TAA-OH with a cation exchange resin and then with a hydrogen halide (eg, hydrochloric acid) is used as a raw material. It can be used as a solution. Therefore, the method of the present invention shown in the above [7] using the raw material solution obtained by such a method is “safe and efficient from an aqueous waste solution containing TAA-OH without electrodialysis or electrolysis. It can recover a TAA-OH aqueous solution with a low impurity content "and is extremely useful as a method for recycling or recycling the waste liquid.

This figure is a diagram schematically showing a process flow of a “raw material solution preparation process” suitable for the method of the present invention. This figure is the figure which showed the process flow of the method of this invention typically.

As described above, an aqueous solution of TAA-OH is useful as various processing agents such as a semiconductor substrate cleaning agent, an etching agent, and a photoresist developer in the manufacture of integrated circuits and large-scale integrated circuits. In a method for recovering and recycling a TAA-OH aqueous solution from the waste liquid of these treatment agents, a method for recovering a TAA-OH aqueous solution with low impurity content safely and efficiently without electrodialysis or electrolysis is known. Not. The method of the present invention not only provides a method for producing TAA-OH from TAA-halogen, but also has an aspect that it can be a main step of a method for recovering an aqueous solution of TAA-OH that can satisfy the above requirements. That is, the method of the present invention can be an industrially excellent method for recovering TAA-OH by including a step of preparing a raw material solution from the waste liquid through a series of steps as shown in FIG.

First, the “raw material solution preparation step” shown in FIG. 1 will be described. In FIG. 1, the H-type cation resin is RZ ⁻ · H ⁺ (R represents a resin part, Z ⁻ represents a cation exchange group, and H ⁺ represents a proton as an example of a cation. ), And the organic impurities contained in the waste liquid are abbreviated as COD. Among the CODs, those that are dissolved in the solution are abbreviated as COD (sol.) And are deposited as solid components or solid components. Those adsorbed on the surface are abbreviated as COD (ab.).

1. Raw Material Solution Preparation Step The raw material solution preparation step shown in FIG. 1 includes a cation exchange resin adsorption step, a TAA-OH washing step, and a desorption step. In the cation exchange resin adsorption step, a cation that is a counter ion of a cation exchange group (—Z ⁻ ) is brought into contact with a cation exchange resin by contacting a waste liquid composed of an aqueous TAA-OH solution containing organic impurities COD (in FIG. 1). Performs ion exchange between H ⁺ ) and a TAA cation (TAA ⁺ ), and fixes (adsorbs) TAA ⁺ to the cation exchange resin. At this time, a part of COD, specifically, COD (sol.) Dissolved in the aqueous solution is separated from TAA ⁺ , but the remaining COD is adsorbed to the cation exchange resin (COD (ab.)). . The TAA-OH washing step is performed to remove COD (ab.) Adsorbed on the cation exchange resin by utilizing the property that COD (ab.) Is easily dissolved in a basic aqueous solution. Since COD (ab.) Is difficult to elute under acidic conditions, this step is not necessarily performed. However, it is preferable to include this step from the viewpoint of regenerating and reusing the cation exchange resin. The reason why the washing is performed with the TAA-OH aqueous solution is that the waste liquid obtained in the washing step can be used as the waste liquid treated in the cation exchange resin adsorption step, so that waste can be reduced (others). When a base is used, it is necessary to finally discard the base.) After the cation exchange resin adsorption step, after passing through a TAA-OH washing step performed as necessary, the cation exchange resin to which TAA ⁺ is immobilized (adsorbed) is a hydrogen halide aqueous solution (for example, Contact with aqueous hydrochloric acid). Such contact occurs ion exchange with ^{H +} derived from TAA ⁺ and hydrogen halide, TAA ⁺ is a halogen derived from the hydrogen halide ^- is recovered as TAA- halogen solution with. The TAA-halogen aqueous solution recovered here is adjusted in concentration as necessary to become a raw material solution. Hereinafter, each step will be described in more detail.

1-1. Cation exchange resin adsorption process (1) Raw material waste liquid As the waste liquid used in the cation exchange resin adsorption process, waste liquids of various treatment agents consisting of TAA-OH aqueous solution used in the semiconductor manufacturing process, liquid crystal display manufacturing process, etc. Can be used. Here, as TAA-OH, tetramethylammonium hydroxide (hereinafter sometimes abbreviated as “TMAH”), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethyl hydroxide Ammonium, trimethylethylammonium hydroxide, dimethyldiethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, triethyl (2-hydroxyethyl) ammonium hydroxide, dimethyldi (2-hydroxyethyl) ammonium hydroxide, diethyldihydroxide (2-hydroxyethyl) ammonium, methyl tri (2-hydroxyethyl) ammonium hydroxide, ethyl tri (2-hydroxyethyl) ammonium hydroxide, tetra (2-hydroxyethyl) hydroxide Le) ammonium, and the like. Among these, TMAH is most widely used.

One typical example of the waste liquid containing TAA-OH is a waste liquid discharged when developing the exposed photoresist with an alkaline developer. The waste liquid contains organic impurities (COD) such as a photoresist in addition to TAA-OH. Photoresist developer wastewater is usually alkaline with a pH of 10 to 14, and photoresist is dissolved in the form of TAA cations and salts in the alkaline developer wastewater by acid groups such as carboxyl groups and hydroxyl groups. Yes. Examples of the main photoresist include indenecarboxylic acid produced by photolysis of the photosensitizing agent o-diazonaphthoquinone and phenols derived from novolac resin.

Further, as another representative waste liquid, there is a waste liquid discharged from a developing process in semiconductor manufacturing and liquid crystal display manufacturing. The waste liquid contains organic impurities such as a photoresist and a surfactant in addition to TAA-OH. However, since the waste liquid contains a large amount of water used in the rinsing process after development, the concentration of each component Has a low feature. For example, the TAA-OH concentration in the waste liquid is about 0.001 to 1% by mass, the photoresist concentration is about 10 to 100 ppm, and the surfactant concentration is about 0 to several tens ppm. In general, in order to recover TAA-OH from waste liquid with such a low TAA-OH content, a concentration operation for evaporating water is required. In this process, TAA ⁺ is selected by ion exchange reaction. Therefore, it is naturally adsorbed by the cation exchange resin, so that the concentration operation is naturally performed (even if the concentration operation by such evaporation is not performed), and TAA ⁺ can be efficiently recovered. Where much heat energy is required to evaporate and remove water, the process has a great advantage in that it does not require such heat energy.

(2) Cation exchange resin The cation exchange resin used in the cation exchange resin adsorption step includes a strongly acidic cation exchange resin in which the ion exchange group is a sulfonic acid group, and a weak acidic cation in which the ion exchange group is a carboxyl group. Known cation exchange resins such as ion exchange resins can be used without particular limitation. The resin structure may be a gel type or a porous type (MP type (macroporous type) or MR type (macroreticular type)). The shape of the resin may be any of powder, granule, film, fiber and the like. In view of processing efficiency, operability, economy and the like, it is preferable to use granular styrene-based or acrylic-based cation exchange resins.

The cation exchange resin is usually marketed in the H or Na type, but the H type is preferable in order to prevent sodium ions from being mixed into the final TAA-OH solution. When using a cation exchange resin commercially available in Na type, first pass an acid such as hydrochloric acid or sulfuric acid through the cation exchange resin before use, thoroughly wash with ultrapure water, and use as H type. Is preferred.

Examples of the cation exchange resin that can be suitably used in this step include Amberlite IRA120B, Amberlite IRC76, Diaion SK1B, Diaion WK40, Purolite C104, Duolite C433LF, Levacit Monoplus S100, Levacit Monoplus CNP80WS , Dowex Marathon C, Muromac C101, Muromac C502, and the like.

(3) Adsorption treatment As a method of bringing the waste liquid containing TAA-OH into contact with the cation exchange resin, a conventionally known method can be appropriately employed depending on the type and shape of the cation exchange resin. For example, when the cation exchange resin is in the form of particles or powder, the packed column (here, the packed column is a concept including a column) is filled with the cation exchange resin and continuously passed through the waste liquid. It is possible to employ a flow method for adding a cation exchange resin to a waste liquid and bringing it into contact with stirring, followed by filtration and solid-liquid separation. Among these methods, it is preferable to adopt a distribution method in consideration of operability. In the case of treating waste liquid having a TAA-OH content of 0.001 to 1% by mass by the flow method, the height (L) and diameter (D) are considered from the viewpoint of TAA ⁺ immobilization efficiency (or adsorption efficiency). ) With a cation exchange resin packed in a packed tower having a ratio (L / D) of 3 to 10 so that the space velocity (SV) is 5 (1 / hour) to 50 (1 / hour). It is preferable to distribute the waste liquid.

The ratio of the total amount of cation exchange groups (-Z ⁻ ) in the cation exchange resin (Z ⁻ / TAA ⁺ ) to the total amount of TAA ⁺ contained in the waste liquid to be treated is 1 (Z ⁻ / TAA ⁺ ). As described above, the amount is preferably selected appropriately from the amount of 1 to 2. When the amount of cation exchange resin to be used is determined, the amount of waste liquid to be used may be adjusted so that the above ratio is 1 or more, preferably 1 to 2. When the amount of the cation exchange resin is small, for example, when the ratio is less than 1, TAA ⁺ is contained in the liquid flowing out through the packed column, so the concentration of TAA ^{+ in} the effluent is reduced. Whether the amount of adsorption is saturated can be confirmed by monitoring, for example, by analyzing by ion chromatography. In addition, when the cation exchange resin is changed from H type to TAA type, the volume swells to about 2 times depending on the type of cation exchange resin. In a fixed case, it can be grasped as a change in the height of the filling region), and it is possible to know a rough adsorption state by observing the situation.

1-2. TAA-OH washing step Since TAA-OH is an organic base, the waste liquid shows basicity. For this reason, organic impurities (COD) such as a resist contained in the waste liquid are dissolved in the waste liquid. However, when the waste liquid comes into contact with the cation exchange resin and ion exchange between TAA ⁺ and H ⁺ proceeds, the basicity of the waste liquid decreases and changes to neutrality. Specifically, the pH is about 10 to 14 The aqueous solution changes from pH 6 to pH 8-8. Therefore, the solubility of organic impurities (COD) is lowered, and a part of the organic impurities (COD) is adsorbed or deposited on the surface or pores of the cation exchange resin. In the raw material solution adjustment step in the present invention, unlike the method described in Patent Document 4, TAA ⁺ adsorbed on the cation exchange resin is desorbed using an aqueous hydrogen halide solution that is an acidic aqueous solution. In the separation step, the organic impurities [COD (ab.)] Adsorbed or precipitated and immobilized [COD (ab.)] Are unlikely to be dissolved and mixed into the desorbed liquid. (Ab.)] May be mixed, and in this case, the purity of the finally obtained TAA-OH may be reduced. In addition, since the organic impurity [COD (ab.)] Is adhered to the cation exchange resin even after the desorption process, when the cation exchange resin regenerated by the desorption process is repeatedly used, TAA ⁺ The adsorptive capacity gradually decreases. The TAA-OH cleaning step is performed in order to avoid such a problem.

In the TAA-OH washing step, the organic impurities [COD (ab.)] Are dissolved and removed in the basic aqueous solution, but the adsorbed TAA ⁺ is not desorbed or mixed with impurities, Furthermore, since the waste liquid after washing can be treated together with the waste liquid used in the adsorption step, and the amount of final waste can be reduced, the basic aqueous solution includes TAA-OH contained in the waste liquid. It is preferable to use an aqueous solution of the same type of TAA-OH, and the concentration of TAA-OH in the aqueous solution is preferably equivalent to that of the waste liquid. The amount of TAA-OH aqueous solution used for washing is preferably 0.2 to 10 times the amount of cation exchange resin on a volume basis, and more preferably 0.5 to 2 times.

1-3. Desorption step In the cation exchange resin adsorption step, TAA cations adsorbed on the cation exchange resin are subjected to a TAA-OH washing step, if necessary, and then desorbed using an aqueous hydrogen halide solution (for example, an aqueous hydrochloric acid solution). Separated (eluted) and recovered as a TAA-halogen aqueous solution. The concentration of the aqueous hydrogen halide solution used in the desorption step may be appropriately selected from the range of 0.01 to 5 N. From the viewpoint of recovering TAA-halogen recovery rate and high-purity TAA-halogen. 0.5 to 2.5 normal is preferable.

As a method of bringing the hydrogen halide aqueous solution into contact with the TAA type cation exchange resin, either a flow method or a batch method may be adopted, but generally, the same method as employed in the cation exchange resin adsorption step. Is preferably adopted.

The amount of hydrogen halide aqueous solution used may be an amount sufficient to desorb (elution) the adsorbed TAA ⁺ , for example, the total amount of cation exchange groups (—Z ⁻ ) in the cation exchange resin (adsorbed). . the TAA ⁺ amount corresponding halogen ions (halogen contained in the hydrogen halide in the aqueous solution used for) ^-) of the ratio (halogen ^- / Z ^-) is 1 to 3, such as preferably a 1.5 to 2 What is necessary is just to select suitably from quantity. Incidentally, the end point of elimination of TAA ⁺ (elution) is sampled with time eluate, TAA ⁺ concentration or the halogen contained in the sampling solution ^- the concentration was analyzed by a method such as ion chromatography monitor by the point TAA ⁺ concentration is not detected, or halogen ^- can be confirmed as a point increased by concentration stops constant.

The concentration of TAA-halogen in the TAA-halogen aqueous solution recovered by such desorption treatment depends on the concentration of the aqueous hydrogen halide solution used, but TAA-OH in the waste liquid used in the cation exchange resin adsorption step. Regardless of the concentration, it is usually in the range of 1 to 20% by mass, preferably 1 to 10% by mass, so that it can be used as it is as a raw material solution in the method of the present invention. When the TAA-halogen concentration is outside the above concentration range, the concentration can be adjusted by concentration or dilution and used as a raw material solution.

2. Method of the Invention In the method of the present invention, TAA-OH is produced from a raw material solution consisting of an aqueous solution in which TAA-halogen is dissolved at a concentration of 1 to 20% by mass using an OH type anion exchange resin. Although it is well known to exchange anionic species of ionic compounds using OH type anion exchange resins, within the knowledge of the present inventors, TAA-halogen to TAA using OH type anion exchange resins. An example of producing —OH is not specifically known. As described above, when the present inventors actually attempted to produce TAA-OH by such a method, the concentration of Cl ions (Cl ⁻ ) contained in the obtained TAA-OH aqueous solution should be 100 ppm or less. Proved difficult.

One of the causes of such a problem may be “equilibrium in the formation reaction”. That is, an OH type anion exchange resin is treated with a Cl type ion exchange resin using an aqueous solution of an inorganic hydroxide such as NaOH as a so-called “regeneration agent”. In such a treatment, regeneration is performed using a regenerant that is several times the theoretical chemical equivalent to the amount of anion exchange groups, and then in the washing liquid. Wash with water until Cl ⁻ is no longer detected. However, if a small amount of unreacted Cl-type anion exchange resin remains in the OH-type anion exchange resin obtained after such treatment, it can be obtained by contacting TAA-halogen with the OH-type anion exchange resin. Since TAA-OH produced has strong basicity, it is considered that TAA-OH once produced by the reaction with the residual Cl-type anionic resin (equilibrium reaction in the production reaction) becomes TAA-Cl. Further, even if an OH type anion exchange resin containing no Cl type is used, a halogen type anion exchange resin is produced by ion exchange of TAA-halogen contained in the raw material solution, and reaction with it. , or halogen contained in the solution ^- by equilibrium reaction with, it is conceivable to become temporarily returns the generated TAA-OH is TAA- halogen.

In order to solve the former problem, when the OH-type anion exchange resin is produced from the Cl-type anion exchange resin, sufficient regeneration treatment may be performed so that no unreacted Cl-type anion exchange resin remains. it is conceivable that. However, Cl liberated in solution in the alkaline processing ^- and OH ^- from the equilibrium reaction between (equilibrium reaction at the time of reproduction), in order to eliminate the residual Cl type anion exchange resin is always the Cl type anion exchange resin It is thought that it is necessary to keep in contact with a fresh inorganic hydroxide aqueous solution (which does not contain Cl 2 ⁻ ), which requires a huge amount of the inorganic hydroxide aqueous solution. Therefore, it is not practical to adopt such a method from the viewpoint of cost and efficiency. The latter problem can be solved by lowering the concentration of TAA-halogen in the aqueous solution brought into contact with the OH-type anion exchange resin. However, reducing the concentration of TAA-halogen in the raw material solution is not possible with TAA- This leads to a decrease in OH production efficiency.

The present invention solves these problems all at once, and a high-concentration TAA-halogen raw material aqueous solution is used for normal purity OH-type anion exchange in which some unreacted Cl-type anion exchange resin may remain. A TAA-OH aqueous solution (primary reaction solution) containing a low concentration of TAA-halogen (or halogen ion) and a low concentration of TAA-Cl (or Cl ion) as an intermediate product is treated with a resin. By treating this with a high-purity OH-type anion exchange resin in which the residual amount of Cl-type anion exchange resin is extremely small, TAA-halogen (or halogen ion) and TAA-Cl (or Cl ion) are obtained. Is intended to obtain a TAA-OH aqueous solution (secondary reaction solution) with an extremely low content of.

According to the method of the present invention, not only can the amount of high-purity OH type anion exchange resin that uses a large amount of inorganic hydroxide in the regeneration treatment to obtain it be reduced as much as possible, A high-purity TAA-OH aqueous solution can be obtained without lowering the TAA-halogen concentration in the raw material solution.

Hereinafter, the method of the present invention will be described with reference to FIG. FIG. 2 is a diagram schematically showing a process flow of the method of the present invention. In FIG. 2, RY ⁺ · Cl ⁻ means “Cl-type anion exchange resin” and R -Y ⁺ · OH ^- means "OH-type anion-exchange resin". R- represents the resin part of the ion exchange resin, and -Y ⁺ represents an anion exchange group. Further, after regenerating the Cl-type anion exchange resin, 100 parts by volume (for example, 100 ml) of the OH-type anion exchange resin obtained after sufficiently washing with water until Cl ions can no longer be detected are packed in the packed tower, Defined as the concentration of Cl ions contained in the final 200 volume parts (for example, 200 ml) of effluent when 500 volume parts (for example, 500 ml) of 0.5 N (N) aqueous sodium hydroxide solution are passed through the packed column OH-type anion-exchange resin having a Cl ion elution amount of less than 100 ppm, preferably less than 60 ppm, and most preferably less than 35 ppm on a mass basis is “OH-type anion-exchange resin”. Normal purity OH type anion exchange resin (OH-typ), abbreviated as “AER (H)” and having a Cl ion elution amount of 100 ppm or more. e-ion-exchange resin) is abbreviated as “OH-AER (N)”.

2-1. Anion exchange resin treatment process [process (A)]
As shown in step of FIG. 2 (A), in the step ^{(A), R-Y +} · Cl - by treating with an inorganic aqueous hydroxide such as NaOH, ^R-Y + · OH ^- a In preparation, two types of RY ⁺ .OH ⁻ having different Cl ion elution amounts, that is, OH-AER (H) and OH-AER (N) are prepared.

(1) Cl-type anion exchange resin A Cl-type anion exchange resin is a resin having an anion exchange group (—Y ⁺ ) and having Cl ⁻ as a counter ion (anion) of the anion exchange group. Means. As the Cl-type anion exchange resin used in the present invention, it is preferable to use a strongly basic anion exchange resin from the viewpoint of ion exchange ability with respect to TAA-Cl when regenerated into OH type. The strongly basic anion exchange resin includes a strongly basic type I anion exchange resin in which the anion exchange group (—Y ⁺ ) is a trimethylammonium group (also simply referred to as type I), and an anion exchange group that is dimethyl There are strong basic type II anion exchange resins (also simply referred to as type II) which are ethanolammonium groups, and any of them may be used in the present invention. The resin part (R-) structure of these anion exchange resins may be a gel type or a porous type (MP type (macroporous type) or MR type (macroreticular type)). The shape of the resin may be any of powder, granule, film, fiber and the like. In view of processing efficiency, operability, economy and the like, it is preferable to use granular anion exchange resin such as styrene or acrylic. Such Cl-type anion exchange resins are commercially available and can be easily obtained.

In general, type I is chemically more stable than type II and has a stronger exchange-adsorption force (selectivity of ions). For example, the selectivity coefficient of Cl ions with respect to type I OH ions is about 10 times that of type II. On the other hand, a large amount of regenerant is required for regeneration, although it is twice as large. On the other hand, since type II has a lower basicity than type I, the ion selectivity is inferior, but the amount of regenerant used can be reduced.

For this reason, in order to reduce the influence of the “equilibrium reaction in the production reaction” in the step (B-2) described later and obtain a higher purity TAA-OH, the OH— used in the step (B-2) As AER (H), it is preferable to use a strongly basic type I anion exchange resin, and it is also preferable to use type I as a Cl type anion exchange resin as a raw material. From the viewpoint of reducing the amount of regenerant used, it is preferable to use type II as the Cl-type anion exchange resin used as a raw material for OH-AER (H) and / or OH-AER (N). . Furthermore, from the viewpoint of obtaining both the effect of increasing the purity of the obtained TAA-OH and the effect of reducing the amount of the regenerant used, it is used in the step (B-1) described later. It is preferable to use type II as OH-AER (H) and / or OH-AER (N) and type I as OH-AER (H) used in step (B-2).

(2) Preparation of OH-AER (N) OH-AER (N) uses an aqueous solution of an inorganic hydroxide as a regenerant and is 1 to several times the theoretical chemical equivalent of Cl type anion exchange resin. Specifically, it can be easily prepared by regenerating with about 1 to 5 times the regenerant. As the inorganic hydroxide, sodium hydroxide (NaOH) or potassium hydroxide (KOH) can be suitably used. The concentration of these hydroxides in the aqueous solution as the regenerant is usually 0.5 to 10% by mass, preferably 1 to 8% by mass.

In order to perform such regeneration, a Cl-type anion exchange resin and a regenerant may be brought into contact with each other, and such contact may employ any method of a so-called batch method or a distribution method. The batch method refers to an OH-type anion exchange resin (unreacted Cl-type anion exchange) regenerated by ion exchange after stirring and mixing a given amount of Cl-type anion exchange resin and a given amount of regenerant in a container. The distribution method is a method of regenerating the OH type by circulating a regenerant through a packed column packed with Cl type anion exchange resin and bringing them into contact with each other. . From the viewpoint of ease of operation and the fact that the step (B) is carried out by a circulation method, it is preferable to adopt a circulation method from the viewpoint that the OH-AER (N) obtained after the regeneration can be used as it is. .

When the flow method is adopted, the packed column packed with Cl-type anion exchange resin has a ratio (L / D) of height (L) to diameter (D) of 3 to 10 from the viewpoint of regeneration efficiency. It is preferable to use a certain one, and the flow rate of the regenerant (inorganic hydroxide aqueous solution) at the time of regeneration is 1 (1 / hour) to 10 (1 / hour) expressed in space velocity (SV). It is preferable.

The amount of regenerant (inorganic hydroxide aqueous solution) to be brought into contact with the Cl-type anion exchange resin depends on the amount of eluted Cl ions allowed, and the anion exchange group (-Y ⁺ ) in the regenerated Cl-type anion exchange resin. of the total amount, or Cl ^- ratio of the total amount of ^- the total amount of, OH contained in the regenerant used ^(OH - / ^{Y +,} or, ^OH - / Cl ^-) is appropriately selected from amounts such that 1 to 5 That's fine. For example, in the case of regenerating using an aqueous NaOH solution as a regenerant by a flow method, the amount of regenerant used is the mass of NaOH (g) [g-NaOH with respect to 1 liter (L) of anion exchange resin. / LR], the amount used when regenerating a strongly basic type I Cl-type anion exchange resin is usually 400 to 800 (g-NaOH / LR). The amount used when regenerating the sex II type Cl anion exchange resin is usually 200 to 400 (g-NaOH / LR).

However, the regeneration rate differs depending on the type of Cl-type anion exchange resin used (for example, whether it is type I or type II), the type and concentration of the regenerant, and the regeneration method and conditions. . Regeneration rate is higher in type II than in type I, and is higher when the concentration of inorganic hydroxide in the regenerant is higher, and when the amount of regenerant used is higher, the regenerant further comes into contact. there is amount including not less than less propensity, in view of overuse prevent regenerant, eluting Cl ion quantity at the time of reproduction in advance actual system ^- Cl contained in the ^- and (Cl amount) and the amount of regenerant It is preferable to investigate the relationship.

Also, the temperature of the regenerant affects the regeneration rate. When the temperature of the regenerant is increased, the regeneration rate can be increased. However, since it is necessary to make the temperature lower than the heat resistant temperature of the Cl-type anion exchange resin, even if the temperature is increased, it is preferably 35 to 40 ° C.

The amount of residual Cl-type anion exchange resin contained in OH-AER (N) (this amount corresponds to the amount of residual Cl ⁻ remaining as a counter ion of the anion exchange group) is represented by OH-AER (H). However, from the viewpoint of reducing the amount of anion exchange resin used, the Cl ion elution amount is preferably 100 to 1500 ppm, more preferably 200 to 1000 ppm, and still more preferably 300 to 1000 ppm on a mass basis. 700 ppm.

(3) Preparation of OH-AER (H) OH-AER (H) can be prepared basically in the same manner as OH-AER (N). However, in order to make the Cl ion elution amount as defined above less than 100 ppm, preferably less than 60 ppm, and most preferably less than 35 ppm, the amount of the regenerant used is increased or Cl ⁻ eluted by regeneration is reduced. It is necessary to take measures such as rapid removal and contact with a fresh regenerant that does not contain Cl 2 ⁻ constantly.

For example, when regenerating by using a NaOH aqueous solution as a regenerant by a flow method, for strong basic type I Cl type anion exchange resin, 800 to 1600 (g-NaOH / LR), strong basic type II OH-AER (H) can be prepared by regenerating with a regenerant of 400 to 800 (g-NaOH / LR) for the type Cl-type anion exchange resin.

In step (A), the preparation of OH-AER (N) and OH-AER (H) may be carried out independently, but can also be carried out simultaneously. When the Cl-type anion exchange resin is regenerated by the flow method, when the regenerant is circulated through the packed tower packed with the Cl-type anion exchange resin, the regenerant is continuously added in the vicinity of the introduction portion of the flow agent. Therefore, Cl ⁻ eluted by the regeneration flows away quickly and constantly comes into contact with a fresh regenerant containing no Cl ⁻ , and OH-AER (H) is easily obtained. In contrast, in the distribution agent discharge the vicinity of the packed column, Cl eluted with regeneration in the upstream part in the regenerant supplied ^- would contain, OH-AER (H) is difficult to obtain, OH -AER (N) is easily obtained. Of course, if the regeneration of the upstream part is completed and the Cl ⁻ from the upstream is removed, the environment near the discharge part becomes the same as the environment near the introduction part, and OH-AER (H) can be obtained. Since Cl ⁻ eluted in the part is considered to move while repeating ion exchange with OH ⁻ , it is necessary to distribute a large amount of a regenerant in order to obtain such an environment in the vicinity of the discharge part. Therefore, when the circulation amount of the regenerant is not sufficient, OH-AER (H) is generated in a region having a certain distance from the introduction portion toward the downstream, and OH-AER ( N) will be produced, and OH-AER (H) and OH-AER (N) will be prepared simultaneously. Step (A) in the method of the present invention includes such an embodiment.

As described above, even if the OH-AER and (H) and OH-AER (N) is prepared simultaneously, remaining Cl in each position in the packed column ^- by checking the concentration, OH @ - AER (H) and OH-AER (N) can also be separated and recovered. Further, when the step (B) is carried out by the distribution method, the introduction port and the discharge port in the regeneration are reversed, the raw material solution is supplied from the discharge port in the regeneration and brought into contact with the OH-AER (N). If the step (B-2) is carried out by carrying out step -1) and bringing it into contact with OH-AER (H) in the vicinity of the inlet for regeneration, the packed tower after regeneration can be used in step (B) as it is. From a different viewpoint, the latter case can also be regarded as a so-called “countercurrent regeneration method” in which the regenerant is fed from the direction opposite to the flow of the raw material solution in the step (B). However, in normal counter-current regeneration, it is not necessary to confirm the amount of Cl-type anion exchange resin remaining slightly in the regenerated OH-type anion exchange resin, and even whether OH-AER (H) is generated. Whereas it is unclear, in the step (A) of the present invention, it is essential to generate a sufficient amount of OH-AER (H) to perform the step (B-2). It is different.

2-2. Reaction process [process (B)]
The reaction step (B) in the method of the present invention includes a step (B-1) and a step (B-2). Here, in the step (B-1), the raw material solution and the normal purity OH type anion exchange resin prepared in the anion exchange resin treatment step (A), or the normal purity OH type anion exchange resin and Primary reaction for obtaining a primary reaction solution comprising a tetraalkylammonium hydroxide aqueous solution containing a tetraalkylammonium halide in a concentration of 0.01 to 1% by mass by contacting with a high purity OH type anion exchange resin. It is a process. In step (B-2), the primary reaction solution is contacted with the high-purity OH type anion exchange resin, and the concentration of the tetraalkylammonium halide is lower than the concentration in the primary reaction solution, And a secondary reaction step of obtaining a secondary reaction solution comprising a tetraalkylammonium hydroxide aqueous solution of less than 0.01% by mass. Hereinafter, the primary reaction step [step (B-1)] and the secondary reaction step [step (B-2)] will be described in detail.

2-3. Primary reaction step [Step (B-1)]
(1) Raw material solution The raw material solution used in the primary reaction step comprises an aqueous solution in which TAA-halogen is dissolved at a concentration of 1 to 20% by mass, preferably 1 to 10% by mass. Here, as the TAA-halogen, those commercially available can be used without any particular limitation. Of TAA-halogens, TAA-Cl is specifically exemplified by tetramethylammonium chloride (TMA-Cl), tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, trimethylethylammonium chloride. Dimethyldiethylammonium chloride, trimethyl (2-hydroxyethyl) ammonium chloride, triethyl (2-hydroxyethyl) ammonium chloride, dimethyldi (2-hydroxyethyl) ammonium chloride, diethyldi (2-hydroxyethyl) ammonium chloride, methyltri (2 -Hydroxyethyl) ammonium, ethyl tri (2-hydroxyethyl) ammonium chloride, tetra (2-hydroxyethyl) ammonium chloride, etc. Door can be. Next, specific examples of TAA-Br include those in which Cl atoms are substituted with Br atoms in the specific examples of TAA-Cl (corresponding bromides). Among these, it is preferable to use TMA-Cl or tetrabutylammonium bromide in view of availability and usefulness of the obtained TAA-OH.

In addition, as the raw material solution, various processing agents composed of an aqueous solution containing TAA-OH, for example, waste liquids such as a semiconductor substrate cleaning agent, an etching agent, and a photoresist developer in the manufacture of integrated circuits and large-scale integrated circuits. A TAA-halogen aqueous solution obtained as a raw material can also be used. The method for preparing the raw material solution from such a waste liquid is as described above.

(2) Production of primary reaction solution In step (B-1), the raw material solution and the OH-type anion exchange resin prepared in step (A) are brought into contact with each other by a batch method, a distribution method or the like, and TAA- An aqueous TAA-OH solution (primary reaction solution) having a halogen concentration of 0.01 to 1% by mass is obtained. At this time, from the viewpoint of overall efficiency and cost reduction, as the OH type anion exchange resin, an OH-AER (N), preferably a type II OH-AER (reducing agent used at the time of regeneration) is used. N) must be used. However, it is not always necessary to use only OH-AER (N), and OH-AER (H) can be used in combination.

When the batch method is employed as the contact method, it is easy to use only OH-AER (N). However, when the flow method is employed, as described above, even in the same packed tower. There may be a region where OH-AER (N) exists and a region where OH-AER (H) exists. In such a case, the raw material solution may be introduced from the region side where OH-AER (N) exists. As the raw material solution passes through the packed tower, the TAA-halogen concentration in the passing raw material solution gradually decreases due to the ion exchange reaction, and instead, the TAA-OH concentration gradually increases. Therefore, when a sufficient amount of the anion exchange resin is present relative to the raw material solution to be circulated, the process (B-1) is performed in the upstream portion, and the process (B- 2) will be performed, but the two steps cannot be clearly separated. Even in such a case, the process (B-1) is performed until the TAA-halogen concentration in the passing raw material solution becomes 0.01 to 1% by mass. At this time, in step (B-1), the raw material liquid may come into contact with OH-AER (H) in the latter half of the step, but such an embodiment is also the step (B) in the method of the present invention. -1).

The amount of the OH type anion exchange resin used in the step (B-1) is appropriately determined according to the contact method, the concentration and amount of the raw material solution to be used, and the like. Even if the raw material solution is brought into contact with an excessive amount of OH-AER (N), it is very difficult to make the TAA-halogen concentration less than 0.01% by mass, so the upper limit of the OH type anion exchange resin is particularly limited. However, excessive use is not preferred due to efficiency. If the amount used is too small, the TAA-halogen concentration cannot be lowered to a predetermined range. For this reason, for example, when employing the batch method, it is preferable to determine the amount of resin required based on the exchange capacity of the OH type anion exchange resin from the concentration and amount of the raw material solution used. In addition, when the distribution method is adopted, since the amount of anion exchange resin that can be used is determined, it is preferable to adjust the amount of the raw material solution to be treated based on the amount and the ion exchange capacity. Regardless of whether the batch method or the distribution method is used as the contact method, step (B-1) can be performed in multiple stages. In this case, the resin amount or the raw material solution amount is adjusted in the same manner. do it. However, the amount of use determined in this way is only a guideline, and in determining the actual amount of use, TAA-halogen concentration is analyzed by appropriately sampling the actual reaction solution, and TAA- It is preferable to grasp the change behavior of the halogen concentration and determine the amount of the anion exchange resin or the raw material solution used based on the result.

The anion exchange resin after the completion of the step (B-1) is in a halogen type, but since it can be used again by performing regeneration, a plurality of packed towers are connected in series particularly in the flow method. Alternatively, a process with high productivity can be assembled by connecting and arranging them in parallel or in combination. For example, when connected in series, the amount of raw material solution that can be processed can be increased, and when connected in parallel, the line is switched to simultaneously perform the process (B-1) and the regeneration process. Since it can be performed, continuous operation is also possible. For these reasons, it is preferable to adopt a distribution method in the step (B-1). When the flow method is adopted, in order to produce TAA-OH efficiently, the packed column has a ratio (L / D) of height (L) to diameter (D) of 3 to 10. It is preferable to use a certain material and distribute the raw material solution so that the space velocity (SV) is 1 (1 / hour) to 10 (1 / hour).

2-4. Secondary reaction step [Step (B-2)]
In the step (B-2), the primary reaction solution obtained in the step (B-1) is contacted with OH-AER (H), preferably type I OH-AER (H), and TAA-halogen is contacted. A TAA-OH aqueous solution (secondary reaction solution) having a concentration lower than the concentration in the primary reaction solution and less than 0.01% by mass is obtained. As described above, due to the influence of the equilibrium reaction, an aqueous solution having a TAA-OH concentration corresponding to the secondary reaction solution cannot be obtained even if the raw material solution is brought into contact with an excessive amount of OH-AER (N). In addition, even when contacting with OH-AER (H), when a raw material solution having a high TAA-halogen concentration is directly contacted, an aqueous TAA-OH solution having a TAA-halogen concentration corresponding to the secondary reaction solution Enormous amounts of OH-AER (H) are required to obtain the product, which is not practical. In the present invention, the influence of the equilibrium reaction is made as much as possible by bringing a primary reaction solution having a low TAA-halogen concentration into contact with OH-AER (H), preferably type I OH-AER (H). And succeeded in obtaining a secondary reaction solution efficiently.

The contact between the primary reaction solution and OH-AER (H) in this step is basically the same as step (B-1) except that the contact target is different. From the viewpoint of process simplicity and efficiency, the contact method is preferably the same as the contact method employed in step (B-1).

When the flow method is adopted in both step (B-1) and step (B-2), OH-AER (H) should be arranged at least in the most downstream part based on the flow direction of the raw material solution. It becomes. For example, when the step (B-1) and the step (B-2) are continuously performed using one packed column, for example, by performing the step (A) as so-called “countercurrent regeneration”, the packing is performed. Since the amount of residual Cl-type anion exchange resin contained in the OH-type anion exchange resin in the column (or the amount of residual halogen-type anion exchange resin) gradually decreases from upstream to downstream, upstream of the packed column OH-AER (N) is arranged in the part, and OH-AER (H) is arranged in the most downstream part. In this case, the distinction between the zone in which the step (B-1) is performed and the zone in which the step (B-2) is performed is not necessarily clear, but at least the most downstream portion includes OH-AER (H) and the secondary If the reaction solution can be recovered, step (B-2) has been performed, and OH-AER (N) is disposed upstream, so in principle (TAA in the column) -Since the halogen concentration gradually decreases), the step (B-1) is performed in the zone upstream of the zone where the step (B-2) was performed. When a plurality of packed towers are connected and installed in series, the OH-type anion exchange resin filled in the most downstream packed tower may be OH-AER (H), and includes the most downstream part. Only the downstream region may be filled with OH-AER (H). When changing the type or type (type I or type II) of the anion exchange resin in the same tower, a Cl type anion exchange resin of a different type or type may be used when the step (A) is regenerated. What is necessary is just to fill in layers. At this time, it is preferable to take measures to prevent the layer structure from changing due to the influence of the liquid flow.

The amount of OH-AER (H) used in step (B-2) is appropriately determined according to the contact method, the concentration and amount of the primary reaction solution used, and the like in step (B-1). That's fine.

Thus the second reaction solution to be recovered is usually from 1 to 15% by weight, an aqueous solution which preferably contains 5-10% by weight of TAA-OH, organic impurities and TAA- halogen (or halide ^-) Alternatively, the content of TAA-Cl (or Cl ⁻ ) is extremely low. For example, even when a raw material solution prepared from the photoresist development waste liquid through the raw material preparation step is used, the concentration of the photoresist component that is an organic impurity can be 50 ppm or less. Such a secondary reaction liquid can be used with various treatment agents as it is depending on the application. Moreover, it can be used by performing relatively simple purification even in applications (treatment agents) that require particularly high purity.

2-5. After the repetition of the production cycle (B), the OH-type anion exchange resin changes to a halogen-type anion exchange resin, but can be reused by performing a regeneration treatment. Therefore, when all the steps (A), (B-1) and (B-2) are carried out by the flow method using the same packed tower, countercurrent regeneration is performed after the series of steps is completed, By making this countercurrent regeneration a new step (A), the production cycle can be repeated. In addition, when a plurality of packed towers are connected and arranged in parallel as described above, the flow path is switched and the process (A) is performed in another packed tower while the process (B) is performed in one packed tower. You can also. Thus, the method of the present invention can be continuously operated, and it can be said that this method is also an industrially excellent method.

In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited to these examples.

In Examples and Comparative Examples shown below, tetramethylammonium hydroxide (TMAH) and tetrabutylammonium hydroxide (TBAH) are used as TAA-OH, and tetramethylammonium chloride (TMAC) is used as TAA-Cl. Tetrabutylammonium chloride (TBAC) was used and tetrabutylammonium bromide (TBAB) was used as TAA-Br. Moreover, as a raw material solution, the solution prepared by the following method from the TMAH aqueous solution which is a photoresist developing waste liquid was used. Furthermore, the concentrations of TMAH, TBAH, TMAC, TBAC, TBAB, Cl ⁻ , Br ⁻ , and organic impurities in the aqueous solution were measured as follows.

(1) Concentration measurement TMAH concentration, TBAH concentration, TMAC concentration, TBAC concentration, TBAB concentration, Cl ⁻ concentration, and Br ⁻ concentration in an aqueous solution were analyzed by ion chromatography. Specifically, ICS2000 manufactured by Dionex is used, ION-pak CS12A is used for the cation analysis column, ION-pak AS15 is used for the anion analysis, and the eluent is methanesulfonic acid for the cation analysis. The anion analysis was performed using potassium hydroxide.
The organic impurity concentration was determined by analyzing the oxygen consumption by potassium permanganate at 100 ° C. (JIS K 0101) and converting it to COD.

(2) Preparation method of raw material solution 1) Cation exchange resin adsorption step First, 100 ml of weakly acidic cation exchange resin Diaion WK40L (manufactured by Mitsubishi Chemical Corporation) is packed into a glass column having a diameter of 22 mm × 750 mm, and Regeneration processing was performed. That is, the cation exchange resin was subjected to ultrapure water cleaning, 1N-HCl cleaning, and ultrapure water cleaning in this order to make the counter ion a hydrogen ion and to form an H type. In addition, the space velocity SV of liquid passing at each cleaning is 5 (1 / hour), and the amount of liquid used in each cleaning step is expressed by the amount of liquid (L) per liter (LR) of resin (R). 10 (L / LR).

Next, 8000 ml of 0.5 mass% TMAH waste liquid (photoresist development waste liquid, mass-based photoresist content: 42 ppm in terms of COD) was passed through the column at a space velocity of SV = 20 (1 / hour).

2) TAA-OH washing step After completion of the adsorption step, 100 ml of 0.5% by mass TMAH aqueous solution is passed through the column at a space velocity of SV = 1 (1 / hour) to remove the resist adsorbed on the cation exchange resin. Washed.

3) Desorption step 800 ml of 1N-HCl was passed through the column washed in the above step at a space velocity of SV = 1 (1 / hour) as an eluent, and the adsorbed TMA ions were eluted as TMAC. The eluate was fractionated in three portions. The first fraction (first fraction) is the eluate from the start of elution until 100 ml flows out, and the second fraction (second fraction) flows out 500 ml after the first fraction. The third fractionation solution (third fractionation solution) is an eluate until 200 ml flows out after the second fractionation. When component concentration analysis was performed on each fraction, the TMAC concentration in the first fraction was 0.1% by mass (0.01 mol / L). Further, the TMAC concentration in the second fractionation solution was 8.3% by mass (0.76 mol / l), and the HCl concentration was 0.1% by mass (0.03 mol / l). The TMAC concentration in the third fractionation solution was 0.5% by mass (0.05 mol / l), and the HCl concentration was 3.5% by mass (0.96 mol / l). The first fraction is considered to contain a large amount of liquid that flows out before the start of desorption, and the third fraction is considered to contain a large amount of eluate that has been desorbed and has flowed out as it is. It is done. Since most of the eluted TMAC was recovered in the second fraction, the second fraction was used as a raw material solution in the examples and comparative examples.

Example 1
(Preparation of normal purity OH type anion exchange resin)
360 ml of a strongly basic (type II) anion exchange resin Amberlite IRA410J (Rohm and Haas) was packed in a glass column having a diameter of 40 mm × 750 mm, and a 0.5 N NaOH (sodium hydroxide) aqueous solution was added at room temperature (20 ° C.). ) At a space velocity SV = 4 (1 / hour). The flow rate was 3600 ml (10 L / LR) and the regeneration level was 200 g-NaOH / LR. Thereafter, 3600 ml (10 L / LR) of ultrapure water was passed at a space velocity SV = 5 (1 / hour) to perform washing. Separately regenerate the OH-type anion exchange resin obtained after sufficient regeneration after taking out from the column and stir well. Collect 100 ml of it and fill it into another column to add 0.5N NaOH. The last effluent that flowed through 500 ml of the aqueous solution was sampled and analyzed. As a result, the Cl ion concentration was 421 ppm, and the normal purity OH type anion exchange resin was prepared by the above regeneration. It was confirmed.

(Preparation of high purity OH type anion exchange resin)
90 ml of strongly basic (type II) anion exchange resin Amberlite IRA410J (made by Rohm and Haas) was packed in a glass column with a diameter of 40 mm × 750 mm, and a space velocity of 0.5N NaOH aqueous solution at room temperature (20 ° C.). The liquid was passed at SV = 4 (1 / hour). The flow rate was 1800 ml (20 L / LR) and the regeneration level was 400 g-NaOH / LR. Thereafter, 900 ml (10 L / LR) of ultrapure water was passed at a space velocity SV = 5 (1 / hour) to perform washing. Separately regenerate the OH-type anion exchange resin obtained by thoroughly washing with water, take out from the column, stir well, and then take 100 ml of it, fill it into another column, and add 0.5N NaOH. Sampling and analysis of 200 ml of the last effluent that passed through 500 ml of aqueous solution, and the analysis revealed that the Cl ion concentration was 29 ppm, and a high-purity OH type anion exchange resin was prepared by the above regeneration. It was confirmed.

(Arrangement of normal purity OH type anion exchange resin and high purity OH type anion exchange resin)
The whole amount of the normal purity OH type anion exchange resin was taken out of the column and packed in the upstream part of the column filled with the high purity OH type anion exchange resin. By carrying out like this, high purity OH type anion exchange resin can be arrange | positioned in the most downstream area | region, and normal purity OH type anion exchange resin can be arrange | positioned in the upstream area | region.

(Contact process with anion exchange resin)
From the upstream part of the column in which the high-purity OH type anion exchange resin is arranged in the most downstream region, 500 ml of the second fraction obtained according to the above-described raw material solution preparation method is passed at a space velocity SV = 4 (1 / hour). did. The eluate was sequentially collected and separated into two liquids. The first 100 ml was used as the first fraction. The first fractionation liquid contained nothing and was treated as a waste liquid because it was water. The second fraction is 400 ml and contains 6.7% by mass (0.74 mol / l) TMAH, 53 ppm (1.5 mmol / l) Cl ion, 15 ppm COD component, and the desired TMAH solution. Met.

Example 2
(Preparation of normal purity OH type anion exchange resin)
A strongly basic (type II) anion exchange resin Amberlite IRA410J (Rohm and Haas) 360 ml was packed in a glass column having a diameter of 40 mm × 750 mm, and 0.5 N NaOH (sodium hydroxide aqueous solution) was added at room temperature (20 ° C.). ) At a space velocity SV = 4 (1 / hour). The flow rate was 3600 ml (10 L / LR) and the regeneration level was 200 g-NaOH / LR. Thereafter, 3600 ml (10 L / LR) of ultrapure water was passed at a space velocity SV = 5 (1 / hour) to perform washing. In addition, as a result of measuring Cl ion elution amount of the obtained OH type anion exchange resin by the same method as in Example 1, it was 478 ppm. Hereinafter, the Cl ion elution amount of the OH type anion exchange resin is measured by the same method as in Example 1.

(Preparation of high purity OH type anion exchange resin)
90 ml of strongly basic (type II) anion exchange resin Amberlite IRA410J (made by Rohm and Haas) was packed in a glass column having a diameter of 40 mm × 750 mm, and 0.5 N NaOH (sodium hydroxide aqueous solution) was added at room temperature (20 ° C.). ) At a space velocity SV = 4 (1 / hour). The flow rate was 1800 ml (20 L / LR) and the regeneration level was 400 g-NaOH / LR. Thereafter, 900 ml (10 L / LR) of ultrapure water was passed at a space velocity SV = 5 (1 / hour) to perform washing. The obtained OH type anion exchange resin had a Cl ion elution amount of 21 ppm.

(Arrangement of normal purity OH type anion exchange resin and high purity OH type anion exchange resin)
A column packed with a normal purity OH-type anion exchange resin was connected in series with a pipe on the upstream side, and a column packed with a high-purity OH-type anion exchange resin on the most downstream side. By carrying out like this, a high purity OH type anion exchange resin can be arrange | positioned in the most downstream area | region.

(Contact process with anion exchange resin)
From the upstream side of the columns connected in series as described above, 500 ml of the second fraction obtained according to the method for preparing the raw material solution was passed at a space velocity SV = 4 (1 / hour). The eluate was sequentially collected and separated into two liquids. The first 100 ml was used as the first fraction. The first fractionation liquid contained nothing and was treated as a waste liquid because it was water. The second fraction is 400 ml and contains 6.8% by mass (0.75 mol / l) TMAH, 48 ppm (1.4 mmol / l) Cl ion, 13 ppm COD component, and the desired TMAH solution. Met.

Example 3
(Preparation of OH type anion exchange resin by counter-current regeneration method)
450 ml of a strongly basic (type II) anion exchange resin Amberlite IRA410J (Rohm and Haas) was packed in a glass tower having a diameter of 40 mm × 750 mm, and 0.5 N NaOH (aqueous sodium hydroxide) was added at room temperature (20 ° C.). ) At a space velocity of SV = 4 (1 / hour). The flow rate is 9000 ml (20 L / LR) and the regeneration level is 400 g-NaOH / LR. Thereafter, 4000 ml (10 L / LR) of ultrapure water was passed from the bottom to the top of the column at a space velocity of SV = 5 (1 / hour) for washing. Using the counter-current regeneration method in this way, it is not necessary to prepare a normal purity OH type anion exchange resin and a high purity OH type anion exchange resin separately and then refill them or connect the column with piping. However, a high purity OH type anion exchange resin can be easily arranged in the most downstream region. At this time, in order to examine whether or not a normal purity OH type anion exchange resin and a high purity OH type anion exchange resin are made, a counter-current regenerated resin is prepared in the same manner as described above. About 100 ml of each resin was taken out and separately packed in a column. 500 ml of 0.5N-NaOH aqueous solution was passed through each column, and the last 200 ml of the passed 0.5N-NaOH aqueous solution was sampled and analyzed. As a result, the Cl ion concentration at the bottom of the column was 36 ppm. It was confirmed that a high purity OH type anion exchange resin was prepared. On the other hand, the Cl ion concentration at the top of the column was 410 ppm, and it was confirmed that a normal purity OH type anion exchange resin was prepared.

(Contact process with anion exchange resin)
From the direction opposite to the direction in which ultrapure water and NaOH aqueous solution were passed through the column of OH type anion exchange resin prepared by the countercurrent regeneration method, from the top of the column to the bottom, according to the above-described method for preparing the raw material solution 500 ml of the obtained second fractionation liquid was passed at a space velocity SV = 4 (1 / hour). The eluate was sequentially collected and separated into two liquids. The first 100 ml was used as the first fraction. The first fractionation liquid contained nothing and was treated as a waste liquid because it was water. The second fraction is 400 ml and contains 6.7% by mass (0.74 mol / l) TMAH, 27 ppm (0.8 mmol / l) Cl ion, 18 ppm COD component, and the desired TMAH solution. Met.

Example 4
(Preparation of OH type anion exchange resin by counter-current regeneration method)
400 ml of strongly basic (type I) anion exchange resin Amberlite IRA400J (Rohm and Haas) was packed in a glass tower having a diameter of 40 mm × 750 mm, and 0.5 N NaOH (sodium hydroxide aqueous solution) was added at room temperature (20 ° C.). ) At a space velocity of SV = 4 (1 / hour). The flow rate is 16000 ml (40 L / LR) and the regeneration level is 800 g-NaOH / LR. Thereafter, 4000 ml (10 L / LR) of ultrapure water was passed from the bottom to the top of the column at a space velocity of SV = 5 (1 / hour) for washing. Using the counter-current regeneration method in this way, it is not necessary to prepare a normal purity OH type anion exchange resin and a high purity OH type anion exchange resin separately and then refill them or connect the column with piping. However, a high purity OH type anion exchange resin can be easily arranged in the most downstream region. At this time, in order to examine whether or not a normal purity OH type anion exchange resin and a high purity OH type anion exchange resin are made, a counter-current regenerated resin is prepared in the same manner as described above. About 100 ml of each resin was taken out and separately packed in a column. 500 ml of 0.5N-NaOH aqueous solution was passed through each column, and the last 200 ml of the passed 0.5N-NaOH aqueous solution was sampled and analyzed. As a result, the Cl ion concentration at the bottom of the column was 57 ppm. It was confirmed that a high purity OH type anion exchange resin was prepared. On the other hand, the Cl ion concentration at the top of the column was 631 ppm, and it was confirmed that a normal purity OH-type anion exchange resin was prepared.

(Contact process with anion exchange resin)
From the direction opposite to the direction in which ultrapure water and NaOH aqueous solution were passed through the column of OH type anion exchange resin prepared by the countercurrent regeneration method, from the top of the column to the bottom, according to the above-described method for preparing the raw material solution 500 ml of the obtained second fractionation liquid was passed at a space velocity SV = 4 (1 / hour). The eluate was sequentially collected and separated into two liquids. The first 100 ml was used as the first fraction. The first fractionation liquid contained nothing and was treated as a waste liquid because it was water. The second fraction is 400 ml and contains 6.9% by mass (0.76 mol / l) TMAH, 20 ppm (0.6 mmol / l) Cl ion, 17 ppm COD component, and the desired TMAH solution. Met.

Comparative Example 1
A strongly basic (type II) anion exchange resin Amberlite IRA410J (made by Rohm and Haas) 450 ml was packed in a glass column having a diameter of 40 mm × 750 mm, and ultrapure water, 1N-NaOH aqueous solution at room temperature (20 ° C.), Ultra pure water was passed in this order, and the counter ion was changed to OH ion. Each liquid was passed at a space velocity of SV = 5 (1 / hour), and the amount of liquid used was 10 L / LR. The regeneration level at this time is 400 g-NaOH / LR. The obtained OH type anion exchange resin had a Cl ion elution amount of 469 ppm, and it was confirmed that a normal purity OH type anion exchange resin was prepared. Through this column, 500 ml of the second fraction obtained in accordance with the above-described raw material solution preparation method was passed at a space velocity of SV = 4 (1 / hour) from the same direction in which ultrapure water and NaOH aqueous solution were passed. did. The eluate was sequentially collected and separated into two liquids. The first 100 ml was used as the first fraction. The first fractionation liquid contained nothing and was treated as a waste liquid because it was water. The second fraction is 400 ml, contains 6.7% by mass (0.74 mol / l) of TMAH, 150 ppm (4.2 mmol / l) of Cl ions, and 13 ppm of COD component, and has a Cl ion concentration. It could not be reduced to 100 ppm or less.

Example 5
(Preparation of OH type anion exchange resin by counter-current regeneration method)
450 ml of strongly basic (type II) anion exchange resin Amberlite IRA410J (Rohm and Haas) is packed in a glass tower having a diameter of 40 mm × 750 mm, and 0.5 N NaOH (sodium hydroxide aqueous solution) is added to 40 ° C. The mixture was heated and passed from the bottom to the top of the column at a space velocity of SV = 4 (1 / hour). The flow rate is 9000 ml (20 L / LR) and the regeneration level is 400 g-NaOH / LR. Thereafter, 4000 ml (10 L / LR) of ultrapure water was passed from the bottom to the top of the column at a space velocity of SV = 5 (1 / hour) for washing. When the countercurrent regeneration method is used in this way, the normal purity OH type anion exchange resin and the high purity OH type anion exchange resin can be prepared separately and then refilled or the column need not be connected by piping. The high-purity OH type anion exchange resin can be easily arranged in the most downstream region. At this time, in order to examine whether or not a normal purity OH type anion exchange resin and a high purity OH type anion exchange resin are made, a counter-current regenerated resin is prepared in the same manner as described above. About 100 ml of each resin was taken out and separately packed in a column. 500 ml of 0.5N-NaOH aqueous solution was passed through each column, and the last 200 ml of the passed 0.5N-NaOH aqueous solution was sampled and analyzed. As a result, the Cl ion concentration at the bottom of the column was 8 ppm. It was confirmed that a high purity OH type anion exchange resin was prepared. On the other hand, the Cl ion concentration at the top of the column was 120 ppm, and it was confirmed that a normal purity OH-type anion exchange resin was prepared.

(Contact process with anion exchange resin)
From the direction opposite to the direction in which ultrapure water and NaOH aqueous solution were passed through the column of the OH type anion exchange resin prepared by the countercurrent regeneration system, the raw material preparation method described in the examples was described. 500 ml of the second fractionation liquid was passed at a space velocity SV = 4 (1 / hour). The eluate was sequentially collected and separated into two liquids. The first 100 ml was used as the first fraction. The first fractionation liquid contained nothing and was treated as a waste liquid because it was water. The second fraction is 400 ml and contains 6.8% by mass (0.75 mol / l) TMAH, 9 ppm (0.25 mmol / l) Cl ion, 16 ppm COD component, and the desired TMAH solution. Met.

Example 6
(Preparation of OH type anion exchange resin by counter-current regeneration method)
450 ml of a strongly basic (type II) anion exchange resin Amberlite IRA410J (Rohm and Haas) was packed in a glass tower having a diameter of 40 mm × 750 mm, and 0.5 N NaOH (aqueous sodium hydroxide) was added at room temperature (20 ° C.). ) At a space velocity of SV = 4 (1 / hour). The flow rate is 9000 ml (20 L / LR) and the regeneration level is 400 g-NaOH / LR. Thereafter, 4000 ml (10 L / LR) of ultrapure water was passed from the bottom to the top of the column at a space velocity of SV = 5 (1 / hour) for washing. When the countercurrent regeneration method is used in this way, the normal purity OH type anion exchange resin and the high purity OH type anion exchange resin can be prepared separately and then refilled or the column need not be connected by piping. The high-purity OH type anion exchange resin can be easily arranged in the most downstream region. At this time, in order to examine whether or not a normal purity OH type anion exchange resin and a high purity OH type anion exchange resin are made, a counter-current regenerated resin is prepared in the same manner as described above. About 100 ml of each resin was taken out and separately packed in a column. 500 ml of 0.5N-NaOH aqueous solution was passed through each column, and the last 200 ml of the passed 0.5N-NaOH aqueous solution was sampled and analyzed. As a result, the Cl ion concentration at the bottom of the column was 32 ppm. It was confirmed that a high purity OH type anion exchange resin was prepared. On the other hand, the Cl ion concentration at the top of the column was 430 ppm, and it was confirmed that a normal purity OH type anion exchange resin was prepared.

(Contact process with anion exchange resin)
550 ml of 10% by mass tetrabutyl chloride from the direction opposite to the direction in which ultrapure water and NaOH aqueous solution were passed through the column of OH type anion exchange resin prepared by the countercurrent regeneration method. An aqueous ammonium solution (0.36 mol / l) was passed at a space velocity of SV = 4 (1 / hour). The eluate was sequentially collected and separated into two liquids. The first 100 ml was used as the first fraction. The first fractionation liquid contained nothing and was treated as a waste liquid because it was water. The second fraction is 450 ml and contains 8.5% by weight (0.33 mol / l) of tetrabutylammonium hydroxide (TBAH), 51 ppm (1.4 mmol / l) of Cl ions. The TBAH solution.

Example 7
(Preparation of OH type anion exchange resin by counter-current regeneration method)
450 ml of a strongly basic (type II) anion exchange resin Amberlite IRA410J (Rohm and Haas) was packed in a glass tower having a diameter of 40 mm × 750 mm, and 0.5 N NaOH (aqueous sodium hydroxide) was added at room temperature (20 ° C.). ) At a space velocity of SV = 4 (1 / hour). The flow rate is 9000 ml (20 L / LR) and the regeneration level is 400 g-NaOH / LR. Thereafter, 4000 ml (10 L / LR) of ultrapure water was passed from the bottom to the top of the column at a space velocity of SV = 5 (1 / hour) for washing. When the countercurrent regeneration method is used in this way, the normal purity OH type anion exchange resin and the high purity OH type anion exchange resin can be prepared separately and then refilled or the column need not be connected by piping. The high-purity OH type anion exchange resin can be easily arranged in the most downstream region. At this time, in order to examine whether or not a normal purity OH type anion exchange resin and a high purity OH type anion exchange resin are made, a counter-current regenerated resin is prepared in the same manner as described above. About 100 ml of each resin was taken out and separately packed in a column. 500 ml of 0.5N-NaOH aqueous solution was passed through each column, and the last 200 ml of the passed 0.5N-NaOH aqueous solution was sampled and analyzed. As a result, the Cl ion concentration at the bottom of the column was 40 ppm. It was confirmed that a high purity OH type anion exchange resin was prepared. On the other hand, the Cl ion concentration at the top of the column was 470 ppm, and it was confirmed that a normal purity OH type anion exchange resin was prepared.

(Contact process with anion exchange resin)
700 ml of 10% by mass tetrabromide bromide from the direction opposite to the direction in which ultrapure water and NaOH aqueous solution were passed through the column of OH type anion exchange resin prepared by the countercurrent regeneration method A butylammonium aqueous solution (0.31 mol / l) was passed at a space velocity SV = 4 (1 / hour). The eluate was sequentially collected and separated into two liquids. The first 100 ml was used as the first fraction. The first fractionation liquid contained nothing and was treated as a waste liquid because it was water. The second fraction was 600 ml, 7.5% by mass (0.29 mol / l) tetrabutylammonium hydroxide (TBAH), 22 ppm (0.62 mmol / L) Cl ion, 5 ppm (0.04 mmol). / L) of the Br ion and the desired TBAH solution.

The method for producing tetraalkylammonium hydroxide of the present invention is suitable for a method of recovering tetraalkylammonium hydroxide in a reusable form from waste liquid obtained after using a developer comprising a tetraalkylammonium hydroxide aqueous solution. Available.

Claims

(A) A Cl-type anion exchange resin having Cl ions as counterions of anion exchange groups and an aqueous inorganic hydroxide solution are contacted to exchange the counterions of the anion exchange groups from Cl ions to OH ions. By preparing an OH type anion exchange resin having an OH ion as a counter ion of the anion exchange group, and (B) the OH type anion exchange prepared in the step. The resin is brought into contact with a raw material solution comprising a tetraalkylammonium halide aqueous solution having a tetraalkylammonium halide concentration of 1 to 20% by mass, and the tetraalkylammonium halide is converted into a tetraalkylammonium hydroxide by an anion exchange reaction. "Reaction process" to convert,
A process for producing a tetraalkylammonium hydroxide comprising
In the anion exchange resin treatment step (A), after contacting the Cl type anion exchange resin with an inorganic hydroxide aqueous solution, the OH type obtained after sufficient washing until Cl ions cannot be detected. 100 parts by volume of anion exchange resin is packed into a packed column, and the final 200 volume parts of the effluent that flows out when 500 volume parts of 0.5 N (N) aqueous sodium hydroxide solution is passed through the packed column. A high-purity OH type anion exchange resin having a Cl ion elution amount defined as the concentration of Cl ions contained is less than 100 ppm and a normal purity OH type anion exchange resin having a Cl ion elution amount of 100 ppm or more are prepared. ,
The reaction step (B)
(B-1) By bringing the raw material solution into contact with the normal purity OH type anion exchange resin, or the normal purity OH type anion exchange resin and the high purity OH type anion exchange resin, A primary reaction step of obtaining a primary reaction solution comprising a tetraalkylammonium hydroxide aqueous solution containing tetraalkylammonium bromide at a concentration of 0.01 to 1% by mass; and
(B-2) The primary reaction solution and the high-purity OH-type anion exchange resin are brought into contact with each other to form a tetraalkylammonium hydroxide aqueous solution having a tetraalkylammonium halide concentration of less than 0.01% by mass. A secondary reaction step for obtaining a secondary reaction solution;
A process for producing a tetraalkylammonium hydroxide, comprising:
The method according to claim 1, wherein the high-purity OH type anion exchange resin used in the step (B-2) is a strongly basic anion exchange resin.
The method according to claim 1, wherein the reaction step (B) is performed by supplying the raw material solution to an ion exchange tower filled with the OH type anion exchange resin prepared in the anion exchange resin treatment step (A). The high-purity OH type anion exchange resin is disposed in the most downstream region of the ion exchange column, and the primary reaction step (B- 1) and performing the secondary reaction step (B-2) in the most downstream region.
A plurality of the ion exchange towers are prepared, the ion exchange towers are connected in series by piping, and the high-purity OH type anion exchange resin is arranged in the whole or the most downstream part of the most downstream ion exchange tower. 3. The method according to 3.
By preparing an ion exchange column filled with a Cl-type anion exchange resin, and circulating an aqueous solution of inorganic hydroxide from the downstream side to the upstream side in the reaction step (B) in the ion exchange column 5. The method according to claim 3, wherein the anion exchange resin treatment step (A) is performed, and the high-purity OH type anion exchange resin is disposed in a most downstream region of the ion exchange column. .
Step (A) in the nth production cycle (where n is a natural number) is repeated by repeating the production cycle comprising the anion exchange resin treatment step (A) and the subsequent reaction step (B). And step (B) are (A n ) and (B n ), respectively, in each anion exchange resin treatment step (A n ) after the second production cycle, the immediately preceding reaction step (B n) 6. The method according to claim 5, wherein the OH-type anion exchange resin converted into a halogen-type anion exchange resin by the anion exchange reaction in -1 ) is regenerated into an OH-type anion exchange resin.
(P-1) A tetraalkylammonium cation as a counter ion of the cation exchange group is brought into contact with a cation exchange resin by contacting an aqueous tetraalkylammonium hydroxide solution in which organic impurities are dissolved with a cation exchange resin. An adsorption process for holding
(P-2) A deionization in which a cation exchange resin having a tetraalkylammonium cation as a counter ion obtained in the adsorption step is contacted with a hydrogen halide to desorb the tetraalkylammonium cation as a tetraalkylammonium halide. Separation process,
The method according to any one of claims 1 to 6, further comprising a raw material solution preparation step (P) comprising: