JPH1099853A - Apparatus for treating water containing tetraalkylammonium hydroxide - Google Patents
Apparatus for treating water containing tetraalkylammonium hydroxideInfo
- Publication number
- JPH1099853A JPH1099853A JP8256755A JP25675596A JPH1099853A JP H1099853 A JPH1099853 A JP H1099853A JP 8256755 A JP8256755 A JP 8256755A JP 25675596 A JP25675596 A JP 25675596A JP H1099853 A JPH1099853 A JP H1099853A
- Authority
- JP
- Japan
- Prior art keywords
- water
- cation exchange
- acidic cation
- taah
- ozone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水酸化テトラアル
キルアンモニウム（以下、ＴＡＡＨという場合がある）
含有水を処理し、ＴＡＡＨと水を回収するための装置に
関するものである。[0001] The present invention relates to a tetraalkylammonium hydroxide (hereinafter sometimes referred to as TAAH).
The present invention relates to an apparatus for treating contained water and recovering TAAH and water.
【０００２】[0002]
【従来の技術】集積回路、液晶装置等の半導体製造工
程、プリント配線基板製造工程などにおけるフォトリソ
グラフィ工程では、フォトレジスト、特にポジ型のフォ
トレジストの現像液として水酸化テトラメチルアンモニ
ウム（以下、ＴＭＡＨという場合がある）等のＴＡＡＨ
が使用されている。このためこれらの工程から排出され
る排水中にはフォトレジスト、ＴＡＡＨおよびこれらの
反応物が含まれており、このうちＴＡＡＨは比率が高く
主成分となっているため、これらの排水はＴＡＡＨ含有
水と呼ばれることがある。2. Description of the Related Art In a photolithography process in a manufacturing process of a semiconductor such as an integrated circuit or a liquid crystal device, a manufacturing process of a printed wiring board, etc., tetramethylammonium hydroxide (hereinafter referred to as TMAH) is used as a developing solution for a photoresist, especially a positive photoresist. TAAH)
Is used. Therefore, the wastewater discharged from these steps contains photoresist, TAAH, and their reactants. Of these, since TAAH has a high ratio and is a main component, these wastewaters contain water containing TAAH. Sometimes called.
【０００３】従来、ＴＡＡＨ含有水の処理方法として、
酸化剤添加下に紫外線処理し、ＲＯ（逆浸透）処理する
方法（特開昭６３−２９４９８９号）、あるいはオゾン
酸化したのちＲＯ処理する方法（特開平７−１３６６５
１号）がある。しかしこれらの方法では、酸化はＲＯ膜
の閉塞を防止するために行っており、ＲＯ処理は排液を
濃縮するために行っているにすぎず、濃縮液は別途処理
を必要とするとともに、有用物の回収も行えないという
問題点がある。Conventionally, as a method of treating TAAH-containing water,
A method of performing an ultraviolet treatment and RO (reverse osmosis) treatment with the addition of an oxidizing agent (Japanese Unexamined Patent Publication (Kokai) No. 63-294989), or a method of performing an RO treatment after ozone oxidation (Japanese Unexamined Patent Publication (Kokai) No. 7-13665)
No. 1). However, in these methods, the oxidation is performed to prevent the RO membrane from being blocked, and the RO treatment is merely performed to concentrate the wastewater, and the concentrated liquid requires a separate treatment and is useful. There is a problem that it is not possible to collect items.
【０００４】一方、ＴＡＡＨを回収する方法として、被
処理液を電気透析する方法がある（特開平７−３２８６
４２号）。しかしこの方法では電解質の導電性を利用し
て通電することにより電解質を移動させて濃縮するもの
であるから、完全にＴＡＡＨを回収することはできず、
また生成する濃縮液を別途処理する必要があり、水の回
収も困難であるという問題がある。On the other hand, as a method of recovering TAAH, there is a method of electrodialyzing a liquid to be treated (JP-A-7-3286).
No. 42). However, in this method, the electrolyte is moved and concentrated by energizing using the conductivity of the electrolyte, so that TAAH cannot be completely recovered.
Further, there is a problem that it is necessary to separately treat the generated concentrated liquid, and it is difficult to collect water.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、簡単
な構成と操作により、効率よくＴＡＡＨおよび水を回収
することが可能な水酸化テトラアルキルアンモニウム含
有水の処理装置を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide an apparatus for treating tetraalkylammonium hydroxide-containing water that can efficiently recover TAAH and water with a simple structure and operation. .
【０００６】[0006]
【課題を解決するための手段】本発明は、水酸化テトラ
アルキルアンモニウム含有水を処理し、水酸化テトラア
ルキルアンモニウムと水を回収するための装置であっ
て、被処理水から水酸化テトラアルキルアンモニウムを
吸着して回収する弱酸性カチオン交換塔と、弱酸性カチ
オン交換塔の処理水をオゾンと反応させて有機物を酸化
分解するオゾン酸化塔と、オゾン酸化塔の処理水を接触
させて低分子の有機物を吸着する活性炭吸着塔と、活性
炭吸着塔の処理水をイオン交換処理する強酸性カチオン
交換樹脂および強塩基性アニオン交換樹脂を用いるイオ
ン交換装置とを備えていることを特徴とする水酸化テト
ラアルキルアンモニウム含有水の処理装置である。SUMMARY OF THE INVENTION The present invention relates to an apparatus for treating tetraalkylammonium hydroxide-containing water and recovering the tetraalkylammonium hydroxide and water. A weakly acidic cation exchange tower that adsorbs and recovers water; an ozone oxidation tower that reacts the treated water of the weakly acidic cation exchange tower with ozone to oxidize and decompose organic substances; An activated carbon adsorption tower for adsorbing organic substances, and an ion exchange device using a strongly acidic cation exchange resin and a strongly basic anion exchange resin for performing ion exchange treatment on the water treated in the activated carbon adsorption tower, It is an apparatus for treating alkylammonium-containing water.
【０００７】本発明において被処理水であるＴＡＡＨ含
有水は、集積回路、液晶装置等の半導体製造工程、プリ
ント配線基板製造工程などにおけるフォトリソグラフィ
工程などから排出されるＴＡＡＨを含有する水であり、
ＴＡＡＨのほかにフォトレジストおよびその反応物その
他の成分が含まれる場合が多い。ＴＡＡＨとしてはＴＭ
ＡＨが含まれる場合が多いが、他のＴＡＡＨが含まれる
場合もある。In the present invention, the TAAH-containing water, which is the water to be treated, is water containing TAAH discharged from a photolithography step in a semiconductor manufacturing process such as an integrated circuit or a liquid crystal device, a printed wiring board manufacturing process, or the like.
In addition to TAAH, a photoresist and its reactants and other components are often included. TM for TAAH
Although AH is often included, other TAAH may be included.
【０００８】弱酸性カチオン交換塔は被処理水からＴＡ
ＡＨを吸着して回収するためのもので、内部に弱酸性カ
チオン交換樹脂層を形成し、これに被処理液路から被処
理水を通液して吸着を行い、吸着を行ったのちに酸を通
液して再生する再生手段を有するように構成される。弱
酸性カチオン交換樹脂はＨ形を用い、通水および再生剤
の通液方向は下向流とするのが好ましいが、逆でもよ
い。弱酸性カチオン交換樹脂はアルカリ性のＴＡＡＨを
容易に吸着し、かつ酸による脱着が容易であるため、効
率よくＴＡＡＨを回収することが可能になる。[0008] The weakly acidic cation exchange column converts TA
AH is for adsorbing and recovering AH. A weakly acidic cation exchange resin layer is formed inside, and water to be treated is passed through a liquid passage to be treated to carry out adsorption. It is configured to have a regenerating means for regenerating by passing the liquid. It is preferable that the weakly acidic cation exchange resin uses H-form, and that the direction of flow of water and the flow of the regenerant is a downward flow, but may be reversed. The weakly acidic cation exchange resin easily adsorbs alkaline TAAH and is easily desorbed by acid, so that TAAH can be efficiently recovered.
【０００９】オゾン酸化塔は弱酸性カチオン交換塔の処
理水を導入し、オゾンと接触させて有機物を酸化分解す
るように構成される。接触方法としては液相中にオゾン
含有ガスを吹込む吹込式、被処理水をスプレーして接触
させるスプレー式、充填材層を介して接触させる充填材
層式などがあげられる。オゾン含有ガスとしては純オゾ
ンガスでもよいが、一般的にはオゾン発生機から得られ
るオゾン化空気が好ましい。[0009] The ozone oxidation tower is configured to introduce the treated water of the weakly acidic cation exchange tower and bring it into contact with ozone to oxidize and decompose organic substances. Examples of the contact method include a blowing method in which an ozone-containing gas is blown into a liquid phase, a spray method in which water to be treated is sprayed and brought into contact, and a filler layer method in which contact is made via a filler layer. The ozone-containing gas may be pure ozone gas, but generally ozonized air obtained from an ozone generator is preferred.
【００１０】活性炭吸着塔は内部に活性炭層を形成し、
オゾン酸化塔の処理水を通液して接触させるように構成
する。活性炭としては粒状活性炭、粉状活性炭など、任
意のものが使用できるが、粒状活性炭が好ましい。通水
方向は下向流が好ましいが、逆でもよい。また活性炭は
加熱処理等により再生して使用可能とする。[0010] The activated carbon adsorption tower forms an activated carbon layer inside,
It is configured so that the treated water of the ozone oxidation tower is passed through and brought into contact. Any activated carbon can be used, such as granular activated carbon and powdered activated carbon, but granular activated carbon is preferred. The water flow direction is preferably a downward flow, but may be reversed. Activated carbon can be regenerated and used by heat treatment or the like.
【００１１】イオン交換装置は強酸性カチオン交換樹脂
および強塩基性アニオン交換樹脂を用いて活性炭処理水
をカチオン交換およびアニオン交換するように構成され
る。このようなイオン交換装置は強酸性カチオン交換樹
脂層を形成したカチオン交換塔と、強塩基性アニオン交
換樹脂層を形成したアニオン交換塔からなる２塔式に構
成するのが一般的であるが、両樹脂層を１塔内に形成し
た複層式、あるいは両樹脂を混合した混床式でもよい。The ion exchange apparatus is configured to perform cation exchange and anion exchange on the activated carbon treated water using a strongly acidic cation exchange resin and a strongly basic anion exchange resin. Such an ion exchange apparatus is generally configured as a two-column system including a cation exchange tower having a strongly acidic cation exchange resin layer formed thereon and an anion exchange tower having a strongly basic anion exchange resin layer formed therein. A multi-layer type in which both resin layers are formed in one tower or a mixed-bed type in which both resins are mixed may be used.
【００１２】強酸性カチオン交換樹脂はＨ形、強塩基性
アニオン交換樹脂はＯＨ形でイオン交換を行い、それぞ
れ酸またはアルカリ再生剤により再生する再生手段を設
ける。強塩基性アニオン交換樹脂はＩ型でもII型でもよ
い。通水は上向流とし、向流再生を行うように構成する
のが好ましいが、他の方向でもよい。A strongly acidic cation exchange resin is ion-exchanged in the H form and a strongly basic anion exchange resin is ion-exchanged in the OH form, and a regenerating means for regenerating with an acid or alkali regenerant is provided. The strongly basic anion exchange resin may be type I or type II. Although it is preferable that the water flow be upward, and that countercurrent regeneration be performed, it may be in another direction.
【００１３】本発明の装置では弱酸性カチオン交換塔の
前に濾過装置、凝集処理等の前処理装置を設けてもよ
く、またイオン交換装置の後にＲＯ装置、殺菌装置等の
後処理装置を設けてもよく、また各塔または装置の中間
に他の処理装置を介在させてもよい。また各塔または装
置の中間、例えばオゾン酸化塔と活性炭吸着塔の中間に
蒸発濃縮器の凝縮などの他の被処理水を導入して混合処
理を行うように構成することも可能である。In the apparatus of the present invention, a pretreatment device such as a filtration device and a coagulation treatment may be provided before the weakly acidic cation exchange column, and a post-treatment device such as a RO device and a sterilization device is provided after the ion exchange device. Alternatively, another treatment device may be interposed between each tower or device. It is also possible to adopt a configuration in which other water to be treated such as condensation of an evaporator is introduced into the middle of each column or apparatus, for example, between the ozone oxidation tower and the activated carbon adsorption tower to perform the mixing treatment.
【００１４】上記の装置による処理方法は、まず被処理
水を弱酸性カチオン交換塔に導入して、被処理水中のＴ
ＡＡＨを弱酸性カチオン交換樹脂に交換吸着させる。こ
の場合、弱酸性カチオン交換樹脂層に被処理液を通液す
ると、破過点まではＴＡＡＨは処理水中にリークしない
ので、被処理液中のＴＡＡＨをほぼ完全に吸着させるこ
とができる。In the treatment method using the above apparatus, first, the water to be treated is introduced into a weakly acidic cation exchange column, and the T
AAH is exchange-adsorbed on a weakly acidic cation exchange resin. In this case, when the liquid to be treated is passed through the weakly acidic cation exchange resin layer, the TAAH does not leak into the treated water until the breakthrough point, so that the TAAH in the liquid to be treated can be almost completely adsorbed.
【００１５】弱酸性カチオン交換樹脂に吸着したＴＡＡ
Ｈは樹脂を酸で再生することにより、塩として回収する
ことができる。すなわちＴＡＡＨは弱酸性カチオン交換
樹脂にトリアルキルアンモニウム（ＴＡＡ）イオンとし
て吸着しているので、これを酸で再生することにより、
ＴＡＡの塩が脱着して回収される。ＴＡＡ塩は加水分解
することによりＴＡＡＨとして回収される。TAA adsorbed on a weakly acidic cation exchange resin
H can be recovered as a salt by regenerating the resin with an acid. That is, since TAAH is adsorbed on the weakly acidic cation exchange resin as a trialkylammonium (TAA) ion, by regenerating this with an acid,
The salt of TAA is desorbed and recovered. The TAA salt is recovered as TAAH by hydrolysis.
【００１６】弱酸性カチオン交換樹脂を再生するための
酸としては塩酸、硫酸などの鉱酸が使用される。上記の
イオン交換および再生の操作は弱酸性カチオン交換樹脂
の通常の操作と同様に行われる。例えば通液方向は上向
流でも下向流でもよく、また再生も向流再生、順流再生
のいずれでもよく、流速も同様に決められる。As an acid for regenerating the weakly acidic cation exchange resin, mineral acids such as hydrochloric acid and sulfuric acid are used. The above-described operations of ion exchange and regeneration are performed in the same manner as the usual operation of a weakly acidic cation exchange resin. For example, the flow direction may be an upward flow or a downward flow, and the regeneration may be either countercurrent regeneration or forward flow regeneration, and the flow rate is determined in the same manner.
【００１７】弱酸性カチオン交換塔の処理水はオゾン酸
化塔に導入してオゾン含有ガスと接触させ、有機物を酸
化分解する。ここで分解される有機物はフォトレジス
ト、その反応物、その他の有機物であり、着色成分を含
む。これらの有機物はそのまま活性炭処理およびイオン
交換処理を行ってもあまり除去できないが、オゾン酸化
することにより酸化分解されて改質され、活性炭処理お
よびイオン交換処理による除去が可能になる。The treated water of the weakly acidic cation exchange tower is introduced into an ozone oxidation tower and brought into contact with an ozone-containing gas to oxidize and decompose organic substances. The organic substance decomposed here is a photoresist, a reaction product thereof, and other organic substances, and includes a coloring component. Although these organic substances cannot be removed much by performing the activated carbon treatment and the ion exchange treatment as they are, they are oxidatively decomposed and reformed by oxidizing with ozone, and can be removed by the activated carbon treatment and the ion exchange treatment.
【００１８】オゾン処理に用いるオゾン量は有機物を完
全に分解する量である必要はなく、改質に必要な量であ
り、含まれる有機物の種類、量その他の条件により異な
るが、一般的には６〜１０ｍｇ−Ｏ3／ｍｇ−ＴＯＣ、
好ましくは８〜９ｍｇ−Ｏ3／ｍｇ−ＴＯＣ程度とされ
る。色度除去のみを目的とする場合は６ｍｇ−Ｏ3／ｍ
ｇ−ＴＯＣでよいが、完全を期すためには８ｍｇ−Ｏ3
／ｍｇ−ＴＯＣの添加が必要である。The amount of ozone used in the ozone treatment does not need to be an amount that completely decomposes organic substances, but is an amount necessary for reforming. The amount of ozone varies depending on the type and amount of organic substances contained and other conditions. 6~10mg-O 3 / mg-TOC ,
Preferably are 8~9mg-O 3 / mg-TOC about. 6 mg-O 3 / m for the purpose of removing chromaticity only
g-TOC is sufficient, but for completeness, 8 mg-O 3
/ Mg-TOC is required.
【００１９】オゾン酸化処理水は活性炭吸着塔に導入し
て活性炭と接触させ、酸化分解により低分子化した有機
物を吸着させる。これにより改質された有機物は活性炭
に吸着されて除去される。活性炭に吸着された有機物は
加熱等の再生工程により除去される。The ozone oxidized water is introduced into an activated carbon adsorption tower and brought into contact with activated carbon to adsorb organic substances that have been reduced in molecular weight by oxidative decomposition. Thereby, the modified organic matter is adsorbed by the activated carbon and removed. Organic matter adsorbed on the activated carbon is removed by a regeneration step such as heating.
【００２０】活性炭吸着塔の処理水はイオン交換装置に
導入してイオン交換および吸着処理を行う。強酸性カチ
オン交換樹脂層ではカチオン交換が行われ、無機のカチ
オンならびにカチオン性の有機物が交換吸着する。強塩
基性アニオン交換樹脂層では、アニオン交換により無機
のアニオンが交換するほか、アニオン性の有機物も吸着
する。これにより活性炭吸着塔で除去されなかった有機
物が吸着されるほか、脱塩も行われ、処理水は純水とし
て回収される。The treated water in the activated carbon adsorption tower is introduced into an ion exchange device to perform ion exchange and adsorption treatment. Cation exchange is performed in the strongly acidic cation exchange resin layer, and inorganic cations and cationic organic substances are exchange-adsorbed. In the strong basic anion exchange resin layer, inorganic anions are exchanged by anion exchange, and anionic organic substances are also adsorbed. This not only adsorbs organic substances not removed in the activated carbon adsorption tower, but also performs desalination and recovers treated water as pure water.
【００２１】強酸性カチオン交換樹脂の再生は塩酸、硫
酸等の酸により、また強塩基性アニオン交換樹脂の再生
は水酸化ナトリウム等のアルカリにより行う。上記の通
水および再生の操作は強酸性カチオン交換樹脂および強
塩基性アニオン交換樹脂を用いる通常のイオン交換装置
と同様に行われる。Regeneration of the strongly acidic cation exchange resin is performed with an acid such as hydrochloric acid or sulfuric acid, and regeneration of the strongly basic anion exchange resin is performed with an alkali such as sodium hydroxide. The above-mentioned operations of water passage and regeneration are performed in the same manner as in a usual ion exchange apparatus using a strongly acidic cation exchange resin and a strongly basic anion exchange resin.
【００２２】上記の処理により、ＴＯＣ２０００ｍｇ／
ｌ前後、色度７０〜９０度、導電率８０００〜９０００
μＳ／ｃｍ、ｐＨ１２のＴＡＡＨ含有水から、ＴＡＡＨ
をほぼ完全に回収し、しかもＴＯＣ０．２〜０．４ｍｇ
／ｌ、色度０度、導電率０．５〜２μＳ／ｃｍ、ｐＨ７
前後の純水を回収することができる。回収したＴＡＡＨ
はそのままフォトリゾグラフィ工程に再利用され、また
純水は洗浄水、ボイラ水、冷却水等に再利用される。By the above processing, TOC 2000 mg /
l, chromaticity 70-90 degrees, conductivity 8000-9000
From TAAH-containing water of μS / cm, pH 12, TAAH
Is almost completely recovered, and the TOC is 0.2 to 0.4 mg.
/ L, chromaticity 0 degree, conductivity 0.5-2 μS / cm, pH7
Pure water before and after can be recovered. TAAH collected
Is reused as it is in the photolithography process, and the pure water is reused as washing water, boiler water, cooling water and the like.
【００２３】[0023]
【発明の実施の形態】以下、本発明の実施の形態を図面
により説明する。図１は実施形態のＴＡＡＨ含有水処理
装置を示す系統図である。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a system diagram showing a TAAH-containing water treatment apparatus according to an embodiment.
【００２４】図１において、１は被処理水槽、２は内部
にＨ形弱酸性カチオン交換樹脂層２ａを形成した弱酸性
カチオン交換塔、３は下部にオゾン吹込装置３ａを有す
るオゾン酸化塔、４は中継槽、５は内部に活性炭層５ａ
を形成した活性炭吸着塔、６は内部にＨ形強酸性カチオ
ン交換樹脂層６ａを形成した強酸性カチオン交換塔、７
は内部にＯＨ形強塩基性アニオン交換樹脂層７ａを形成
した強塩基性アニオン交換塔である。これらは被処理水
路１１、連絡路１２〜１７および処理水路１８によりシ
リーズに連絡している。強酸性カチオン交換塔６と強塩
基性アニオン交換塔７はイオン交換装置を構成してい
る。In FIG. 1, 1 is a water tank to be treated, 2 is a weakly acidic cation exchange tower having an H-type weakly acidic cation exchange resin layer 2a formed therein, 3 is an ozone oxidation tower having an ozone blowing device 3a in the lower part, Is a relay tank and 5 is an activated carbon layer 5a inside.
Is an activated carbon adsorption tower, 6 is a strongly acidic cation exchange column having an H-type strongly acidic cation exchange resin layer 6a formed inside,
Is a strong basic anion exchange tower having an OH type strong basic anion exchange resin layer 7a formed therein. These are connected to the series by the to-be-treated water channel 11, the communication channels 12 to 17, and the treated water channel 18. The strongly acidic cation exchange column 6 and the strongly basic anion exchange column 7 constitute an ion exchange device.
【００２５】８は凝縮水槽、９は内部にＨ形強酸性カチ
オン交換樹脂層９ａを形成したアンモニア除去塔であ
り、これらは凝縮水路２１、連絡路２２によりシリーズ
に連絡し、連絡路２３により中継槽４に連絡している。
この系路は超純水製造システム等の再生排液その他の排
液を蒸発濃縮する工程から凝縮水が生成する場合に、任
意的に設けられるものである。Reference numeral 8 denotes a condensed water tank, and 9 denotes an ammonia removing tower having an H-type strongly acidic cation exchange resin layer 9a formed therein. These are connected to a series by a condensed water passage 21 and a communication passage 22 and relayed by a communication passage 23. Tank 4 is in contact.
This system is arbitrarily provided when condensed water is generated from the step of evaporating and condensing the regenerated effluent and other effluents in an ultrapure water production system or the like.
【００２６】弱酸性カチオン交換塔２およびアンモニア
除去塔９は下向流通水、下向流再生、活性炭吸着塔５は
下向流通水、強酸性カチオン交換塔６および強塩基性ア
ニオン交換塔７は上向流通水、下向流再生となるように
通液および再生手段が形成されているが、詳細な図示は
省略されている。The weakly acidic cation exchange tower 2 and the ammonia removal tower 9 are downward flowing water, downward flow regeneration, the activated carbon adsorption tower 5 is downward flowing water, the strong acidic cation exchange tower 6 and the strong basic anion exchange tower 7 are The flow-through and regeneration means are formed so as to achieve upward flow water and downward flow regeneration, but detailed illustration is omitted.
【００２７】上記の装置による処理方法は、まず被処理
水路１１から被処理水槽１に導入され貯留されている被
処理水を、連絡路１２から弱酸性カチオン交換塔２に導
入して下向流で通水し、被処理水中のＴＡＡＨを弱酸性
カチオン交換樹脂層２ａに交換吸着させる。この場合、
弱酸性カチオン交換樹脂層２ａに被処理水を通水する
と、破過点まではＴＡＡＨは処理水中にリークしないの
で、被処理水中のＴＡＡＨをほぼ完全に吸着させること
ができる。In the treatment method using the above-described apparatus, first, the water to be treated, which is introduced from the treated water channel 11 into the treated water tank 1 and stored therein, is introduced into the weakly acidic cation exchange column 2 through the communication line 12 and flows downward. To exchange and adsorb TAAH in the water to be treated to the weakly acidic cation exchange resin layer 2a. in this case,
When the water to be treated is passed through the weakly acidic cation exchange resin layer 2a, the TAAH does not leak into the treated water until the breakthrough point, so that the TAAH in the treated water can be almost completely adsorbed.
【００２８】弱酸性カチオン交換樹脂層２ａに吸着した
ＴＡＡＨは樹脂を酸で再生することによりＴＡＡの塩と
して回収することができる。すなわちＴＡＡＨは弱酸性
カチオン交換にＴＡＡイオンとして吸着しているので、
これを酸で再生することによりＴＡＡの塩が脱着して回
収される。ＴＡＡ塩は加水分解することによりＴＡＡＨ
として回収される。弱酸性カチオン交換樹脂を再生する
ための酸としては塩酸、硫酸などの酸が使用される。上
記のイオン交換および再生の操作は弱酸性カチオン交換
樹脂を用いる通常のイオン交換塔の操作とほぼ同様の条
件で行われる。TAAH adsorbed on the weakly acidic cation exchange resin layer 2a can be recovered as a salt of TAA by regenerating the resin with an acid. That is, since TAAH is adsorbed as TAA ions in weakly acidic cation exchange,
By regenerating this with an acid, the salt of TAA is desorbed and recovered. TAA salt is converted into TAAH by hydrolysis.
Will be collected as Acids such as hydrochloric acid and sulfuric acid are used as the acid for regenerating the weakly acidic cation exchange resin. The above-mentioned operations of ion exchange and regeneration are carried out under substantially the same conditions as those of an ordinary ion exchange column using a weakly acidic cation exchange resin.
【００２９】弱酸性カチオン交換塔２の処理水は連絡路
１３からオゾン酸化塔３に導入し、オゾン含有ガス路１
９から供給されオゾン吹込装置３ａから吹込まれるオゾ
ン含有ガスと接触させ、有機物を酸化分解する。ここで
分解される有機物はフォトレジスト、その反応物、その
他の有機物であり、着色成分も分解される。これらの有
機物はオゾン酸化により低分子化合物に分解され活性炭
およびイオン交換樹脂により吸着される形態に改質され
る。The treated water of the weakly acidic cation exchange tower 2 is introduced into the ozone oxidation tower 3 through the communication line 13 and
The organic matter is oxidized and decomposed by contact with an ozone-containing gas supplied from the ozone blowing device 3a supplied from the ozone blowing device 3a. The organic substance decomposed here is a photoresist, a reaction product thereof, and other organic substances, and the coloring component is also decomposed. These organic substances are decomposed into low molecular compounds by ozone oxidation and reformed into a form that is adsorbed by activated carbon and an ion exchange resin.
【００３０】オゾン含有ガス路１９に供給されるオゾン
含有ガスは、オゾン発生機によりオゾン濃度を高めたオ
ゾン化空気が用いられる。オゾン処理に用いるオゾン量
は有機物を完全に分解する量である必要はなく、含まれ
る有機物の種類、量その他の条件により異なるが、一般
的には６〜１０ｍｇ−Ｏ3／ｍｇ−ＴＯＣ、好ましくは
８〜９ｍｇ−Ｏ3／ｍｇ−ＴＯＣ程度の改質に必要な量
とされる。As the ozone-containing gas supplied to the ozone-containing gas passage 19, ozonized air whose ozone concentration is increased by an ozone generator is used. The amount of ozone used for ozone treatment does not need to be an amount that completely decomposes organic substances, and varies depending on the type, amount, and other conditions of the organic substances contained, but is generally 6 to 10 mg-O 3 / mg-TOC, preferably is the amount required to 8~9mg-O 3 / mg-TOC of about reforming.
【００３１】オゾン酸化処理水は連絡路１４から中継槽
４に導入し、ここで必要により連絡路２３から導入され
る凝縮水と混合される。中継槽４の被処理水は連絡路１
５から活性炭吸着塔５に導入し、活性炭層５ａに下向流
で通して接触させ、オゾンの酸化分解により低分子化し
た有機物を吸着させる。これによりオゾン酸化塔３で改
質された有機物は活性炭層５ａに吸着されて除去され
る。活性炭に吸着された有機物は加熱等による活性炭の
再生工程により分解除去される。The ozone oxidized water is introduced into the relay tank 4 from the communication path 14, where it is mixed with condensed water introduced from the communication path 23 as necessary. The water to be treated in the relay tank 4 is the communication channel 1
5 into the activated carbon adsorption tower 5 and is brought into contact with the activated carbon layer 5a in a downward flow to adsorb organic substances that have been reduced in molecular weight by oxidative decomposition of ozone. Thereby, the organic matter reformed in the ozone oxidation tower 3 is adsorbed and removed by the activated carbon layer 5a. Organic substances adsorbed on the activated carbon are decomposed and removed in a step of regenerating the activated carbon by heating or the like.
【００３２】活性炭吸着塔５の処理水は連絡路１６から
強酸性カチオン交換塔６に導入し、上向流で強酸性カチ
オン交換樹脂層６ａに通水してカチオン交換および吸着
処理を行う。強酸性カチオン交換樹脂層６ａではカチオ
ン交換が行われ、無機のカチオンならびにカチオン性の
有機物が交換吸着する。強酸性カチオン交換塔６の処理
水は連絡路１７から強塩基性アニオン交換塔７に導入
し、強塩基性アニオン交換樹脂層７ａに上向流で通水す
る。強塩基性アニオン交換樹脂層７ａでは、アニオン交
換により無機のアニオンのほか、アニオン性の有機物も
吸着する。これにより、活性炭吸着塔５で除去されなか
った有機物が吸着されるほか、脱塩も行われ、処理水は
処理水路１８から純水として回収される。The treated water of the activated carbon adsorption tower 5 is introduced into the strongly acidic cation exchange tower 6 from the communication path 16 and is passed upward through the strongly acidic cation exchange resin layer 6a to perform cation exchange and adsorption treatment. Cation exchange is performed in the strongly acidic cation exchange resin layer 6a, and inorganic cations and cationic organic substances are exchange-adsorbed. The treated water of the strongly acidic cation exchange column 6 is introduced into the strongly basic anion exchange column 7 through the communication path 17 and flows upward through the strongly basic anion exchange resin layer 7a. The strongly basic anion exchange resin layer 7a adsorbs not only inorganic anions but also anionic organic substances by anion exchange. As a result, the organic matter not removed in the activated carbon adsorption tower 5 is adsorbed, desalting is performed, and the treated water is recovered as pure water from the treated water passage 18.
【００３３】強酸性カチオン交換樹脂層６ａの再生は塩
酸、硫酸等の酸により、また強塩基性アニオン交換樹脂
層７ａの再生は水酸化ナトリウム等のアルカリにより行
う。上記の通水および再生の操作は強酸性カチオン交換
樹脂および強塩基性アニオン交換樹脂を用いる通常のイ
オン交換装置とほぼ同様の条件で行う。The strongly acidic cation exchange resin layer 6a is regenerated with an acid such as hydrochloric acid or sulfuric acid, and the strongly basic anion exchange resin layer 7a is regenerated with an alkali such as sodium hydroxide. The above-mentioned operations of water passage and regeneration are carried out under substantially the same conditions as those of an ordinary ion exchange apparatus using a strongly acidic cation exchange resin and a strongly basic anion exchange resin.
【００３４】クローズトシステムでは、超純水製造シス
テム、その他の再生排液や他の排液を蒸発濃縮して凝縮
水を回収利用するが、このような凝縮水は凝縮水路２１
から凝縮水槽８に導入して貯留する。凝縮水槽８の凝縮
水は連絡路２２からアンモニア除去塔９に導入し、強酸
性カチオン交換樹脂層９ａに下向流で通水し、アンモニ
アその他のカチオンを除去する。その処理水は連絡路２
３から中継槽４に導入し、オゾン処理水と混合し、以降
の処理に供する。In the closed system, the ultrapure water production system and other regenerated effluents and other effluents are evaporated and concentrated to recover and utilize the condensed water.
From the condensed water tank 8 for storage. The condensed water in the condensed water tank 8 is introduced into the ammonia removing tower 9 from the communication path 22 and flows downward through the strongly acidic cation exchange resin layer 9a to remove ammonia and other cations. The treated water is connected to channel 2.
From 3, it is introduced into the relay tank 4, mixed with the ozonized water, and provided for the subsequent processing.
【００３５】上記の処理では、ＴＡＡＨ含有水を弱酸性
カチオン交換塔２で処理することにより、被処理除去水
中のＴＡＡＨをほぼ完全に回収し再利用することができ
る。そしてＴＡＡＨを除去した被処理水はオゾン酸化塔
３においてオゾン酸化することにより、有機物を活性炭
およびイオン交換樹脂で吸着可能な成分に改質すること
ができる。改質された有機物等の分解物は活性炭吸着塔
５で除去される。ここで除去されなかった有機物等は強
酸性カチオン交換塔６および強塩基性アニオン交換塔７
からなるイオン交換装置で除去され、このイオン交換装
置ではさらに脱塩も行われ、純水が回収される。In the above-described treatment, the TAAH-containing water is treated in the weakly acidic cation exchange column 2 so that the TAAH in the water to be treated can be almost completely recovered and reused. Then, the water to be treated from which TAAH has been removed is subjected to ozone oxidation in the ozone oxidation tower 3 so that organic substances can be reformed into components that can be adsorbed by activated carbon and ion exchange resin. Decomposed products such as reformed organic substances are removed in the activated carbon adsorption tower 5. The organic substances not removed here are removed from the strongly acidic cation exchange column 6 and the strongly basic anion exchange column 7
, And the deionization is further performed in this ion exchange device to recover pure water.
【００３６】[0036]
実施例１ 図１の処理装置（ただし凝縮水処理系を除く）において
ＴＭＡＨ：２９００ｍｇ／ｌ、導電率：９０５０μＳ／
ｃｍ、ＴＯＣ：２２００ｍｇ／ｌ、色度：７２度、ｐＨ
１２．２のＴＡＡＨ含有水を処理した。弱酸性カチオン
交換塔２は弱酸性カチオン交換樹脂Ｌｅｗａｔｉｔ（バ
イエル社、商標）ＣＮＰ８０を６８０１ｍｌ充填し、硫
酸再生、流速ＳＶ＝１．１ｈｒ-1、活性炭吸着塔５は活
性炭クラレコール（株式会社クラレ、商標）ＫＷ１０／
３２を２００ｍｌ充填し、流速ＳＶ＝３．７ｈｒ-1、強
酸性カチオン交換塔６は強酸性カチオン交換樹脂Ｌａｗ
ａｔｉｔ ＳＰ１１２ ＷＳを２００ｍｌ充填し、硫酸
再生、流速ＳＶ＝３．７ｈｒ-1、強塩基性アニオン交換
塔７は強塩基性アニオン交樹樹脂ＬｅｗａｔｉｔＭ５０
０ ＷＳを２００ｍｌ充填し、水酸化ナトリウム再生、
流速ＳＶ＝３．７ｈｒ-1で処理を行った。オゾン酸化塔
３におけるオゾン吹込量は８ｍｇ−Ｏ3／ｍｇ−ＴＯＣ
である。Example 1 TMAH: 2900 mg / l, conductivity: 9050 μS / in the treatment apparatus of FIG. 1 (excluding the condensed water treatment system)
cm, TOC: 2200 mg / l, chromaticity: 72 degrees, pH
12.2 TAAH-containing water was treated. The weakly acidic cation exchange column 2 is filled with 6801 ml of weakly acidic cation exchange resin Lewatit (Bayer, Inc.) CNP80, sulfuric acid regeneration, flow rate SV = 1.1 hr −1 , and the activated carbon adsorption column 5 is activated carbon Kuraray Coal (Kuraray Co., Ltd. Trademark) KW10 /
32 was 200ml filled, the flow rate SV = 3.7hr -1, a strongly acidic cation exchange column 6 is strongly acidic cation exchange resins Law
Atit SP112 WS was filled with 200 ml, sulfuric acid regeneration, flow rate SV = 3.7 hr -1 , strong basic anion exchange column 7 was a strong basic anion exchange resin Lewatit M50.
0 WS filled 200 ml, sodium hydroxide regeneration,
The treatment was performed at a flow rate SV of 3.7 hr -1 . Ozone blowing amount in the ozone oxidation column 3 is 8mg-O 3 / mg-TOC
It is.
【００３７】処理結果を表１に示す。Table 1 shows the processing results.
【表１】 [Table 1]
【００３８】比較例１ 実施例１において、オゾン酸化を行わなかった場合の結
果を表２に示す。Comparative Example 1 Table 2 shows the results obtained in Example 1 when ozone oxidation was not performed.
【表２】 [Table 2]
【００３９】以上の結果より、ＴＡＡＨは弱酸性カチオ
ン交換塔によりほぼ完全に回収でき、またオゾン処理に
より他の有機物を含む不純物が改善されて活性炭および
イオン交換処理により効率的に除去され高純度の水を回
収できることがわかる。From the above results, TAAH can be almost completely recovered by the weakly acidic cation exchange column, and impurities including other organic substances are improved by the ozone treatment, and are efficiently removed by the activated carbon and the ion exchange treatment. It can be seen that water can be recovered.
【００４０】[0040]
【発明の効果】本発明によれば、ＴＡＡＨ含有水を弱酸
性カチオン交換塔で処理したのち、オゾン酸化塔で処理
し、さらに活性炭吸着塔およびイオン交換装置において
処理するように構成したので、簡単な構成と操作によ
り、効率よくＴＡＡＨをほぼ完全に回収できるととも
に、他の有機物を含む不純物は改質して吸着等により除
去でき、これにより高純度の水を回収することができ
る。According to the present invention, since TAAH-containing water is treated in a weakly acidic cation exchange column, then treated in an ozone oxidation column, and further treated in an activated carbon adsorption column and an ion exchange device, the present invention is simple. With a simple configuration and operation, TAAH can be efficiently and almost completely recovered, and impurities including other organic substances can be reformed and removed by adsorption or the like, whereby high-purity water can be recovered.
【図１】実施形態のＴＡＡＨ含有水処理装置を示す系統
図である。FIG. 1 is a system diagram showing a TAAH-containing water treatment apparatus according to an embodiment.
１ 被処理水槽 ２ 弱酸性カチオン交換塔 ３ オゾン酸化塔 ４ 中継槽 ５ 活性炭吸着塔 ６ 強酸性カチオン交換塔 ７ 強塩基性アニオン交換塔 ８ 凝縮水槽 ９ アンモニア除去塔 １１ 被処理水路 １２〜１７、２２、２３ 連絡路 １８ 処理水路 １９ オゾン含有ガス路 ２１ 凝縮水路 DESCRIPTION OF SYMBOLS 1 To-be-processed water tank 2 Weakly acidic cation exchange tower 3 Ozone oxidation tower 4 Relay tank 5 Activated carbon adsorption tower 6 Strongly acidic cation exchange tower 7 Strongly basic anion exchange tower 8 Condensed water tank 9 Ammonia removal tower 11 Treated water channels 12-17,22 , 23 communication path 18 treated water path 19 ozone-containing gas path 21 condensed water path
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０２Ｆ 9/00 ５０２ Ｃ０２Ｆ 9/00 ５０２Ｊ ５０２Ｒ ５０３ ５０３Ｃ ５０４ ５０４Ｂ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C02F 9/00 502 C02F 9/00 502J 502R 503 503C 504 504B
Claims (1)
水を処理し、水酸化テトラアルキルアンモニウムと水を
回収するための装置であって、 被処理水から水酸化テトラアルキルアンモニウムを吸着
して回収する弱酸性カチオン交換塔と、 弱酸性カチオン交換塔の処理水をオゾンと反応させて有
機物を酸化分解するオゾン酸化塔と、 オゾン酸化塔の処理水を接触させて低分子の有機物を吸
着する活性炭吸着塔と、 活性炭吸着塔の処理水をイオン交換処理する強酸性カチ
オン交換樹脂および強塩基性アニオン交換樹脂を用いる
イオン交換装置とを備えていることを特徴とする水酸化
テトラアルキルアンモニウム含有水の処理装置。1. An apparatus for treating tetraalkylammonium hydroxide-containing water and recovering the tetraalkylammonium hydroxide and water, wherein the weakly acidic apparatus absorbs and recovers the tetraalkylammonium hydroxide from the water to be treated. A cation exchange tower, an ozone oxidation tower that reacts the treated water of the weakly acidic cation exchange tower with ozone to oxidize and decompose organic substances, and an activated carbon adsorption tower that contacts the treated water of the ozone oxidation tower to adsorb low molecular organic substances. An apparatus for treating tetraalkylammonium hydroxide-containing water, comprising: a strongly acidic cation exchange resin for treating the treated water of the activated carbon adsorption tower with an ion exchange treatment; and an ion exchange apparatus using a strongly basic anion exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8256755A JPH1099853A (en) | 1996-09-27 | 1996-09-27 | Apparatus for treating water containing tetraalkylammonium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8256755A JPH1099853A (en) | 1996-09-27 | 1996-09-27 | Apparatus for treating water containing tetraalkylammonium hydroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1099853A true JPH1099853A (en) | 1998-04-21 |
Family
ID=17297001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8256755A Pending JPH1099853A (en) | 1996-09-27 | 1996-09-27 | Apparatus for treating water containing tetraalkylammonium hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1099853A (en) |
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| JP2005329315A (en) * | 2004-05-19 | 2005-12-02 | Japan Organo Co Ltd | Method and apparatus for recovering water from drainage containing tetraalkyl ammonium ion |
| JP2007098240A (en) * | 2005-10-03 | 2007-04-19 | Kurita Water Ind Ltd | Nonionic surfactant-containing water treatment method and apparatus |
| JP2007098272A (en) * | 2005-10-04 | 2007-04-19 | Kobelco Eco-Solutions Co Ltd | Ammonia-containing water treatment method and apparatus |
| JP2011012044A (en) * | 2009-06-03 | 2011-01-20 | Tokuyama Corp | Method for producing tetraalkylammonium hydroxide |
| WO2011074495A1 (en) * | 2009-12-15 | 2011-06-23 | 株式会社トクヤマ | Method for reusing waste liquid from which tetraalkylammonium ions have been removed |
| KR101258730B1 (en) | 2007-04-25 | 2013-05-02 | 가부시키가이샤 도쿠야마 | Method for the treatment of tetraalkylammonium ion-containing development waste liquor |
| JP2014531300A (en) * | 2011-08-25 | 2014-11-27 | ターサノ・インコーポレーテッド | Treatment of water to extend the half-life of ozone |
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1996
- 1996-09-27 JP JP8256755A patent/JPH1099853A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005329315A (en) * | 2004-05-19 | 2005-12-02 | Japan Organo Co Ltd | Method and apparatus for recovering water from drainage containing tetraalkyl ammonium ion |
| JP4561967B2 (en) * | 2004-05-19 | 2010-10-13 | オルガノ株式会社 | Method and apparatus for recovering water from waste water containing tetraalkylammonium ions |
| JP2007098240A (en) * | 2005-10-03 | 2007-04-19 | Kurita Water Ind Ltd | Nonionic surfactant-containing water treatment method and apparatus |
| JP2007098272A (en) * | 2005-10-04 | 2007-04-19 | Kobelco Eco-Solutions Co Ltd | Ammonia-containing water treatment method and apparatus |
| KR101258730B1 (en) | 2007-04-25 | 2013-05-02 | 가부시키가이샤 도쿠야마 | Method for the treatment of tetraalkylammonium ion-containing development waste liquor |
| JP2011012044A (en) * | 2009-06-03 | 2011-01-20 | Tokuyama Corp | Method for producing tetraalkylammonium hydroxide |
| WO2011074495A1 (en) * | 2009-12-15 | 2011-06-23 | 株式会社トクヤマ | Method for reusing waste liquid from which tetraalkylammonium ions have been removed |
| JP2011125770A (en) * | 2009-12-15 | 2011-06-30 | Tokuyama Corp | Method for recycling treated waste liquid |
| CN102686520A (en) * | 2009-12-15 | 2012-09-19 | 德山株式会社 | Method for reusing waste liquid from which tetraalkylammonium ions have been removed |
| JP2014531300A (en) * | 2011-08-25 | 2014-11-27 | ターサノ・インコーポレーテッド | Treatment of water to extend the half-life of ozone |
| JP2015142915A (en) * | 2011-08-25 | 2015-08-06 | ターサノ・インコーポレーテッド | Treatment of water to extend half-life of ozone |
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