WO2011036942A1 - Procédé de production d'hydroxyde de tétraalkylammonium - Google Patents

Procédé de production d'hydroxyde de tétraalkylammonium Download PDF

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WO2011036942A1
WO2011036942A1 PCT/JP2010/062700 JP2010062700W WO2011036942A1 WO 2011036942 A1 WO2011036942 A1 WO 2011036942A1 JP 2010062700 W JP2010062700 W JP 2010062700W WO 2011036942 A1 WO2011036942 A1 WO 2011036942A1
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exchange resin
anion exchange
taa
type anion
type
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PCT/JP2010/062700
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English (en)
Japanese (ja)
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誠 佐藤
淳 渡邉
昭子 村田
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株式会社トクヤマ
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Priority to CN2010800409348A priority Critical patent/CN102510853A/zh
Priority to JP2011532934A priority patent/JPWO2011036942A1/ja
Publication of WO2011036942A1 publication Critical patent/WO2011036942A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

Definitions

  • 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.
  • TAA-OH Tetraalkylammonium hydroxide
  • 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.
  • it has been studied to recover TAA-OH from waste liquid and reuse it.
  • 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).
  • TAA cation tetraalkylammonium cation
  • TAA-Cl tetraalkylammonium chloride
  • TAA perchlorate tetraalkylammonium 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).
  • 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.
  • a special dedicated facility is required to perform electrodialysis or electrolysis.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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
  • 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.
  • 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.
  • 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).
  • 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.
  • a raw material solution preparation step (P) comprising:
  • TAA-halogen concentration can be manufactured.
  • 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.
  • the reaction step (B) 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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. ),
  • the organic impurities contained in the waste liquid are abbreviated as COD.
  • COD 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.).
  • 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.
  • a 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.
  • 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).
  • 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).
  • 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.
  • 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.
  • TAA-OH tetramethylammonium hydroxide
  • TMAH tetramethylammonium hydroxide
  • TMAH tetraethylammonium hydroxide
  • tetrapropylammonium 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
  • 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.
  • COD organic impurities
  • 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.
  • main photoresist include indenecarboxylic acid produced by photolysis of the photosensitizing agent o-diazonaphthoquinone and phenols derived from novolac resin.
  • the 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.
  • the concentration of each component Has a low feature.
  • 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
  • the surfactant concentration is about 0 to several tens ppm.
  • a concentration operation for evaporating water is required.
  • 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.
  • 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.
  • H type is preferable in order to prevent sodium ions from being mixed into the final TAA-OH solution.
  • 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.
  • 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.
  • the packed column here, the packed column is a concept including a column
  • the packed 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.
  • the height (L) and diameter (D) are considered from the viewpoint of TAA + immobilization efficiency (or adsorption efficiency).
  • 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 + ).
  • the amount is preferably selected appropriately from the amount of 1 to 2.
  • the amount of waste liquid to be used may be adjusted so that the above ratio is 1 or more, preferably 1 to 2.
  • 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.
  • 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.
  • 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.
  • COD organic impurities
  • 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.
  • TAA + adsorbed on the cation exchange resin is desorbed using an aqueous hydrogen halide solution that is an acidic aqueous solution.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • TAA-halogen to TAA using OH type anion exchange resins.
  • An example of producing —OH is not specifically known.
  • the concentration of Cl ions (Cl ⁇ ) contained in the obtained TAA-OH aqueous solution should be 100 ppm or less. Proved difficult.
  • 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”.
  • 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.
  • a regenerant that is several times the theoretical chemical equivalent to the amount of anion exchange groups
  • 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.
  • 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.
  • 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.
  • 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.
  • FIG. 2 is a diagram schematically showing a process flow of the method of the present invention.
  • RY + ⁇ Cl ⁇ means “Cl-type anion exchange resin”
  • R -Y + ⁇ OH - means "OH-type anion-exchange resin”.
  • R- represents the resin part of the ion exchange resin
  • -Y + represents an anion exchange group.
  • OH-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”.
  • OH-typ 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)”.
  • Anion exchange resin treatment process 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.
  • 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.
  • 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
  • strong basic type II anion exchange resins also simply referred to as type II
  • 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.
  • type I is chemically more stable than type II and has a stronger exchange-adsorption force (selectivity of ions).
  • 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.
  • regenerant On the other hand, a large amount of regenerant is required for regeneration, although it is twice as large.
  • type II since type II has a lower basicity than type I, the ion selectivity is inferior, but the amount of regenerant used can be reduced.
  • step (B-1) 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).
  • 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.
  • an inorganic hydroxide sodium hydroxide (NaOH) or potassium hydroxide (KOH) can be suitably used.
  • 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.
  • 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. .
  • 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.
  • 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).
  • 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.
  • the temperature of the regenerant affects the regeneration rate.
  • the regeneration rate can be 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).
  • 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.
  • 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.
  • strong basic type II OH-AER H
  • strong basic type II OH-AER H
  • step (A) the preparation of OH-AER (N) and OH-AER (H) may be carried out independently, but can also be carried out simultaneously.
  • 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.
  • Step (A) in the method of the present invention includes such an embodiment.
  • 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.
  • 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).
  • countercurrent 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.
  • the reaction step (B) in the method of the present invention includes a step (B-1) and a step (B-2).
  • 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.
  • the primary reaction step [step (B-1)] and the secondary reaction step [step (B-2)] will be described in detail.
  • 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.
  • TAA-halogen those commercially available can be used without any particular limitation.
  • TAA-halogens TAA-halogens, TAA-Cl is specifically exemplified by tetramethylammonium chloride (TMA-Cl), tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, trimethylethylammonium chloride.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the contact method 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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).
  • 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).
  • 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).
  • 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.
  • 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.
  • 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.
  • the OH-type anion exchange resin filled in the most downstream packed tower may be OH-AER (H), and includes the most downstream part.
  • OH-AER H
  • 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.
  • step (B-2) 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.
  • 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 -)
  • the content of TAA-Cl (or Cl ⁇ ) is extremely low.
  • 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.
  • 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.
  • 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.
  • the method of the present invention can be continuously operated, and it can be said that this method is also an industrially excellent method.
  • TMAH tetramethylammonium hydroxide
  • TMAC tetramethylammonium chloride
  • TBAC Tetrabutylammonium chloride
  • TBAB tetrabutylammonium bromide
  • 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.
  • the TMAC concentration in the first fraction was 0.1% by mass (0.01 mol / L).
  • 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.
  • Amberlite IRA410J Amberlite IRA410J
  • Amberlite IRA410J 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 a
  • 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.
  • a high purity OH type anion exchange resin can be arrange
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • TBAH tetrabutylammonium hydroxide
  • 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.
  • TBAH tetrabutylammonium hydroxide
  • 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.

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Abstract

Le procédé de production d'une solution aqueuse d'hydroxyde de tétraalkylammonium (TAA-OH) ci-décrit consiste à mettre une résine échangeuse d'anions de type OH, obtenue par régénération d'une résine échangeuse d'ions de type Cl, en contact avec une solution de matière première comprenant de 1 à 20 % en poids d'une solution aqueuse de chlorure de tétraalkylammonium (TAA-Cl). Dans le procédé selon l'invention, une résine échangeuse d'anions de type OH qui est obtenue par une technique de régénération couramment utilisée et a une teneur de résidus Cl relativement importante est mise en contact avec la solution de matière première pour obtenir une première solution réactionnelle comprenant une solution aqueuse de TAA-OH ayant une concentration de TAA-Cl de 0,01 à 1 % en poids, et cette première solution réactionnelle est mise en contact avec une résine échangeuse d'anions de type OH ayant une teneur de résidus Cl extrêmement basse pour obtenir une solution aqueuse de TAA-OH ayant une concentration de TAA-Cl inférieure à 0,01 % en poids. C'est ainsi qu'un procédé de production de TAA-OH peut être obtenu, ledit procédé étant applicable à un procédé de collecte d'une solution aqueuse de TAA-OH ayant une basse teneur d'impuretés, sans danger et à une efficacité élevée, à partir de déchets liquides aqueux contenant du TAA-OH sans avoir à recourir à une électrophorèse ou à une électrolyse.
PCT/JP2010/062700 2009-09-24 2010-07-28 Procédé de production d'hydroxyde de tétraalkylammonium WO2011036942A1 (fr)

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WO2012090699A1 (fr) * 2010-12-28 2012-07-05 株式会社トクヤマ Procédé de production d'un sel de tétraalkylammonium, et procédé de production d'un hydroxyde de tétraalkylammonium utilisant celui-ci comme matière première
CN108911287A (zh) * 2018-07-23 2018-11-30 华进半导体封装先导技术研发中心有限公司 用于集成电路制造的清洗液再生工艺方法与装置
CN117486728A (zh) * 2023-12-28 2024-02-02 山东国邦药业有限公司 一种高效循环的氟化试剂及其制备方法与应用

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CN104278288A (zh) * 2014-09-30 2015-01-14 赵文洲 一种连续电解制备高纯四丁基氢氧化铵的方法
CN105294455B (zh) * 2015-10-09 2017-10-27 南京工业大学 阴离子交换制备四丁基氢氧化铵水溶液的方法
CN109206322A (zh) * 2018-09-21 2019-01-15 南京元亨化工科技有限公司 一种基于扩散渗析的四丙基氢氧化铵的提纯方法
CN110158114B (zh) * 2019-05-31 2020-10-27 中触媒新材料股份有限公司 一种制备四烷基氢氧化铵的三膜四室电解系统和方法
CN110644014B (zh) * 2019-10-30 2020-06-30 盐城泛安化学有限公司 一种四乙基氢氧化铵的制备方法
CN113929586B (zh) * 2021-11-24 2024-04-19 江苏科技大学 一种半导体材料及其制备方法

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WO2012090699A1 (fr) * 2010-12-28 2012-07-05 株式会社トクヤマ Procédé de production d'un sel de tétraalkylammonium, et procédé de production d'un hydroxyde de tétraalkylammonium utilisant celui-ci comme matière première
CN108911287A (zh) * 2018-07-23 2018-11-30 华进半导体封装先导技术研发中心有限公司 用于集成电路制造的清洗液再生工艺方法与装置
CN117486728A (zh) * 2023-12-28 2024-02-02 山东国邦药业有限公司 一种高效循环的氟化试剂及其制备方法与应用
CN117486728B (zh) * 2023-12-28 2024-05-17 山东国邦药业有限公司 一种高效循环的氟化试剂及其制备方法与应用

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