JPH07136651A - Treatment of waste solution containing tetraalkylammonium hydroxide - Google Patents
Treatment of waste solution containing tetraalkylammonium hydroxideInfo
- Publication number
- JPH07136651A JPH07136651A JP5285099A JP28509993A JPH07136651A JP H07136651 A JPH07136651 A JP H07136651A JP 5285099 A JP5285099 A JP 5285099A JP 28509993 A JP28509993 A JP 28509993A JP H07136651 A JPH07136651 A JP H07136651A
- Authority
- JP
- Japan
- Prior art keywords
- reverse osmosis
- waste liquid
- soln
- osmosis membrane
- waste
- 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.)
- Granted
Links
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水酸化テトラメチルア
ンモニウム等の水酸化テトラアルキルアンモニウム廃液
の処理方法に関し、とくにフォトリソグラフィーにおい
てフォトレジストの現像液として使用されているアルカ
リ性物質である水酸化テトラアルキルアンモニウム含有
廃液の逆浸透膜を使用した処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a tetraalkylammonium hydroxide waste liquid such as tetramethylammonium hydroxide, and in particular tetrahydroxide which is an alkaline substance used as a developer for photoresist in photolithography. The present invention relates to a method for treating an alkylammonium-containing waste liquid using a reverse osmosis membrane.
【０００２】[0002]
【従来の技術】水酸化テトラアルキルアンモニウムは、
集積回路、液晶表示装置等の半導体装置の製造をはじめ
として各種のフォトリソグラフィー工程においてフォト
レジストの現像液として使用されており、また電池等の
アルカリ性電解質、分析試薬としても使用されている。
水酸化テトラアルキルアンモニウムを含有する廃液は、
強アルカリ性であるとともに、テトラアルキルアンモニ
ウム化合物が自然界では分解しにくい窒素を含有した有
機物質であるとともに、各種の有機物等を含有している
ので、廃液を酸で中和しても、そのまま放流することは
できず各種の処理を施していた。2. Description of the Related Art Tetraalkylammonium hydroxide is
It is used as a developing solution for photoresists in various photolithography processes including manufacturing semiconductor devices such as integrated circuits and liquid crystal display devices, and is also used as an alkaline electrolyte for batteries and analytical reagents.
The waste liquid containing tetraalkylammonium hydroxide is
In addition to being strongly alkaline, the tetraalkylammonium compound is an organic substance containing nitrogen that is difficult to decompose in nature, and contains various organic substances, so it is discharged as it is even if the waste liquid is neutralized with an acid. It could not be done, and various treatments were performed.
【０００３】テトラアルキルアンモニウム含有廃液の処
理は、水酸化テトラメチルアンモニウムをはじめとする
テトラアルキルアンモニウム化合物、フォトレジスト成
分であるノボラック樹脂、感光材料等の高分子物質、界
面活性剤等の各成分を燃焼することによって行われてい
る。ところが、テトラアルキルアンモニウム含有廃液は
多量の水分を含んでいるため、燃焼用の熱エネルギーの
ほとんどは水分の蒸発に用いられることになる。The waste liquid containing tetraalkylammonium is treated with tetraalkylammonium compounds such as tetramethylammonium hydroxide, novolak resins as photoresist components, polymer substances such as photosensitive materials, and various components such as surfactants. It is done by burning. However, since the tetraalkylammonium-containing waste liquid contains a large amount of water, most of the thermal energy for combustion is used to evaporate the water.
【０００４】そこで、廃液の容量を減少させるために水
酸化テトラアルキルアンモニウムを含有する廃液のｐＨ
を９〜１２に調整し、逆浸透膜に加圧供給して濃縮する
ことによって廃液の容量を減少する処理方法（特開昭６
０−１１８２８２号公報）も提案されているが、アルカ
リ性では逆浸透膜の寿命が短くなることが避けられず、
また廃液中のレジストの種類によってはｐＨの調整の際
に析出するものもあり、廃液中に混在する界面活性剤や
その他の成分によっては、逆浸透膜の性能を著しく劣化
させる場合もある。Therefore, in order to reduce the volume of the waste liquid, the pH of the waste liquid containing tetraalkylammonium hydroxide is
Is adjusted to 9 to 12, the pressure is supplied to the reverse osmosis membrane under pressure, and the concentration is reduced to reduce the volume of the waste liquid (Japanese Patent Laid-Open No. Sho 6-62,091).
No. 0-118282) is also proposed, but it is unavoidable that the life of the reverse osmosis membrane is shortened under alkaline conditions.
Further, some of the resists in the waste liquid may precipitate during the pH adjustment, and depending on the surfactant and other components mixed in the waste liquid, the performance of the reverse osmosis membrane may be significantly deteriorated.
【０００５】また、水酸化テトラアルキルアンモニウム
含有廃液を、硫酸、塩酸、その他の酸により中性もしく
は弱酸性とし、レジスト等を析出させて濾過膜、沈降分
離等の方法によって析出物を除去後、逆浸透膜に加圧供
給して濃縮し、廃液の容量を減少する処理方法も考えら
れるが、レジストの析出物は微粒子であるとともに粘性
が大きく、濾過速度や沈降速度が遅く完全な分離が困難
であった。また、析出物を完全に分離しないで逆浸透膜
に供給した場合には、逆浸透膜の性能を低下させるとい
う問題もあった。また、水酸化テトラアルキルアンモニ
ウムを分解する微生物を使用して、水酸化テトラアルキ
ルアンモニウムを分解した後に、活性汚泥処理によって
残存する有機物を処理する方法も知られているが、微生
物による分解方法は、分解に長時間を要するとともに、
微生物の管理が難しく、さらには大がかりな設備を要す
るという問題がある。Further, the tetraalkylammonium hydroxide-containing waste liquid is neutralized or weakly acidified with sulfuric acid, hydrochloric acid or another acid to deposit a resist or the like, and after removing the deposit by a method such as a filtration membrane or sedimentation separation, A treatment method is possible in which pressure is supplied to the reverse osmosis membrane to concentrate and reduce the volume of the waste liquid, but the precipitates of the resist are fine particles and have a high viscosity, and the filtration speed and sedimentation speed are slow, and complete separation is difficult. Met. Further, when the precipitate is supplied to the reverse osmosis membrane without being completely separated, there is a problem that the performance of the reverse osmosis membrane is deteriorated. Further, using a microorganism that decomposes tetraalkylammonium hydroxide, after decomposing the tetraalkylammonium hydroxide, a method of treating organic matter remaining by activated sludge treatment is also known. It takes a long time to disassemble,
There is a problem that it is difficult to control microorganisms and large-scale equipment is required.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、多量の水分
と数％以下の水酸化テトラアルキルアンモニウムなどの
テトラアルキルアンモニウム化合物を含有した廃液を、
逆浸透膜の性能劣化や目詰まりを起こすことなく効率よ
く加圧供給し、廃液を濃縮して容量を減少することを課
題とするものであり、逆浸透膜に悪影響を及ぼさないｐ
Ｈ域において逆浸透膜の利用を可能とするものである。SUMMARY OF THE INVENTION The present invention provides a waste liquid containing a large amount of water and a few% or less of a tetraalkylammonium compound such as tetraalkylammonium hydroxide.
The problem is to efficiently pressurize the reverse osmosis membrane without causing performance deterioration or clogging and to concentrate the waste liquid to reduce the volume, which does not adversely affect the reverse osmosis membrane.
This makes it possible to use the reverse osmosis membrane in the H region.
【０００７】[0007]
【課題を解決するための手段】水酸化テトラアルキルア
ンモニウム含有廃液の処理方法において、該廃液中の有
機物を酸化処理によって低分子化あるいは分解するする
とともにｐＨ６〜８に中和処理した後に、逆浸透膜に加
圧供給して廃液中の水分を分離する処理方法である。ま
た、酸化処理をオゾンによって行うとともに、中和処理
を二酸化炭素の注入によって行う処理方法である。In a method for treating a tetraalkylammonium hydroxide-containing waste liquid, reverse osmosis is carried out after an organic substance in the waste liquid is reduced to a low molecular weight or decomposed by oxidation treatment and neutralized to pH 6-8. This is a treatment method of supplying water to the membrane under pressure to separate water in the waste liquid. Further, it is a treatment method in which the oxidation treatment is performed by ozone and the neutralization treatment is performed by injecting carbon dioxide.
【０００８】すなわち、本発明は現像廃液などの水酸化
テトラアルキルアンモニウムを含有する有機物含有アル
カリ性廃液を、有機物を酸化処理するとともにアルカリ
を中和した後に、逆浸透膜に加圧供給して有機物含有廃
液を濃縮する廃液の処理方法である。本発明の方法は、
逆浸透膜に加圧供給する前に、水酸化テトラアルキルア
ンモニウム含有廃液を、酸化剤によって酸化処理し含ま
れている高分子物質等を低分子化あるいは分解した後
に、さらに中和処理を行い次いで逆浸透処理を行うもの
であり、中和処理の際には水酸化テトラアルキルアンモ
ニウム含有廃液中から析出物が生じることはないので、
逆浸透膜に供給する前に析出物の分離工程を設ける必要
はなく、逆浸透処理操作を確実に行うことができ、ま
た、廃液を中和しているので逆浸透膜には悪影響を及ぼ
すことはない。That is, according to the present invention, an organic substance-containing alkaline waste liquid containing a tetraalkylammonium hydroxide such as a developing waste liquid is supplied to the reverse osmosis membrane under pressure after the organic substance is oxidized and the alkali is neutralized. This is a waste liquid treatment method for concentrating the waste liquid. The method of the present invention is
Before supplying under pressure to the reverse osmosis membrane, the tetraalkylammonium hydroxide-containing waste liquid is oxidized with an oxidizing agent to lower the molecular weight or decompose the high molecular substances contained in it, and then further neutralize it. Reverse osmosis treatment is performed, and during the neutralization treatment, precipitates do not occur from the tetraalkylammonium hydroxide-containing waste liquid, so
The reverse osmosis treatment operation can be performed reliably without the need for a separation process of the precipitate before supplying it to the reverse osmosis membrane, and the reverse osmosis membrane is adversely affected because the waste liquid is neutralized. There is no.
【０００９】図１は本発明の方法を説明するための図で
ある。水酸化テトラアルキルアンモニウムを含有する現
像廃液は、ｐＨ１２〜１４のアルカリ性を有しているが
ｐＨの調整等は行わずに、廃液貯槽１からポンプ４で加
圧して酸化処理装置５に送られる。酸化処理装置では、
酸化剤発生装置２あるいは酸化剤貯槽から送られて来る
酸化剤によって酸化処理が行われる。酸化処理装置で
は、高分子物質であるフォトレジストあるいは感光剤を
酸化分解によって低分子化するとともに、界面活性剤や
その他の有機物を分解する。酸化剤として、オゾン、過
酸化水素水、水の電気分解によって発生するオゾン含有
水、次亜塩素酸塩、二酸化塩素、塩素等の酸化力の大き
な酸化剤を廃液中へ添加する酸化剤による方法、紫外線
ランプ等を用いて紫外線を照射する方法等によって行う
ことができ、また酸化剤による処理方法と紫外線の照射
とを併用しても良い。オゾン、過酸化水素水、水の電気
分解によって発生するオゾン含有水等のように、酸素あ
るいは酸素と水素のみからなる物質を使用した場合に
は、廃液中には酸素原子、水素原子以外は持ち込まれな
いので、廃液の燃焼処理を行う場合には、排ガスの処理
が容易である。また、オゾンを使用した場合には、ｐＨ
が高いのでオゾンの寿命は非常に短く、酸化処理後の廃
液中にオゾンが残存することはないが、過酸化水素、次
亜塩素酸塩等の酸化剤を使用した場合には、廃液中に残
留しないように添加量を厳密に調整したり、あるいは残
留した酸化剤を分解することが必要となる。FIG. 1 is a diagram for explaining the method of the present invention. The developing waste liquid containing tetraalkylammonium hydroxide has an alkalinity of pH 12 to 14, but the pH is not adjusted and the waste liquid storage tank 1 pressurizes it with a pump 4 and sends it to the oxidation treatment apparatus 5. In the oxidation treatment equipment,
Oxidizing treatment is performed by the oxidizing agent sent from the oxidizing agent generator 2 or the oxidizing agent storage tank. In the oxidation treatment device, a high molecular weight photoresist or photosensitizer is decomposed into a low molecular weight by oxidative decomposition, and a surfactant and other organic substances are decomposed. As an oxidant, ozone, hydrogen peroxide solution, ozone-containing water generated by electrolysis of water, hypochlorite, chlorine dioxide, chlorine and other oxidizing agents with large oxidizing power are added to the waste liquid. It can be carried out by a method of irradiating ultraviolet rays using an ultraviolet lamp or the like, and the method of treatment with an oxidizing agent and irradiation of ultraviolet rays may be used in combination. When using oxygen or a substance consisting of only oxygen and hydrogen, such as ozone, hydrogen peroxide, or ozone-containing water generated by electrolysis of water, bring in only oxygen and hydrogen atoms into the waste liquid. Therefore, the exhaust gas can be easily treated when the waste liquid is burnt. When ozone is used, the pH
The ozone has a very short life, so ozone does not remain in the waste liquid after the oxidation treatment, but when an oxidizing agent such as hydrogen peroxide or hypochlorite is used, It is necessary to strictly adjust the amount of addition so as not to remain, or to decompose the remaining oxidizing agent.
【００１０】次に、有機物を酸化処理した廃液に中和処
理工程６において、酸貯槽３から供給される酸を添加し
てｐＨ６〜８にまで中和処理を行う。中和処理工程では
既にフォトレジストあるいは感光剤の分子は低分子化し
ており廃液中からは析出しない。中和処理には、二酸化
炭素、あるいは硫酸、塩酸等の各種の酸を用いることが
できるが、硫酸、塩酸等の強酸を使用する場合には、酸
の添加量が当量となるように調整することが必要であ
り、塩の増加による浸透圧の上昇を引き起こすという問
題が生じ、また廃液中の水分量が増加することとなる。
これに対し、二酸化炭素の場合には過剰に注入してもテ
トラアルキルアンモニウム塩の緩衝作用のためにｐＨは
６以下にはならず、過剰の二酸化炭素により溶存気体が
増加しても逆浸透膜の透過にはなんら障害とならず、ま
た廃液中の水分を増加させることはない。Next, in the neutralization treatment step 6, the acid supplied from the acid storage tank 3 is added to the waste liquid obtained by subjecting the organic matter to the oxidation treatment to neutralize it to pH 6-8. In the neutralization process step, the molecules of the photoresist or the photosensitizer have already been reduced and do not precipitate from the waste liquid. For the neutralization treatment, carbon dioxide or various acids such as sulfuric acid and hydrochloric acid can be used. When a strong acid such as sulfuric acid and hydrochloric acid is used, the amount of acid added is adjusted to be the equivalent amount. Therefore, there is a problem that an increase in salt causes an increase in osmotic pressure, and the amount of water in the waste liquid increases.
On the other hand, in the case of carbon dioxide, the pH does not become 6 or less due to the buffering action of the tetraalkylammonium salt even if it is injected excessively, and even if the dissolved gas increases due to the excess carbon dioxide, the reverse osmosis membrane It does not hinder the permeation of water and does not increase the water content in the waste liquid.
【００１１】中和工程の後に、逆浸透循環貯槽７から高
圧ポンプ８によって逆浸透膜９に加圧供給され、透過水
１０が取り出されるとともに、濃縮液は逆浸透循環貯槽
へ循環され、連続的に廃液から水分を分離することがで
きる。逆浸透膜の性能劣化を引き起こす有機物、酸化剤
は既に分解されており、また目詰まりを起こす析出微粒
子も存在しないので、長期にわたり効率的な濃縮が行わ
れる。After the neutralization step, the reverse osmosis circulation storage tank 7 is pressurized and supplied to the reverse osmosis membrane 9 by the high-pressure pump 8 and the permeated water 10 is taken out, and the concentrated liquid is circulated to the reverse osmosis circulation storage tank and continuously. It is possible to separate water from waste liquid. Organic substances and oxidants that cause deterioration of the performance of the reverse osmosis membrane have already been decomposed, and there are no precipitated fine particles that cause clogging, so that efficient concentration can be performed for a long time.
【００１２】一方、水酸化テトラアルキルアンモニウム
含有廃液を酸化処理の前に中和処理を行っても良い。こ
の場合には、フォトレジストおよび感光剤等の高分子物
質の微粒子が析出するが、次いで酸化処理を行うことに
よって、高分子物質の低分子化あるいは有機物の分解に
よって析出物は消失する。中和処理には、二酸化炭素、
硫酸、塩酸等の酸を使用することができるが、二酸化炭
素を使用することが好ましい。酸化処理の際には、酸化
剤が残留しないように酸化剤を分解することが必要とな
るが、中和に二酸化炭素を使用するとともに酸化剤とし
てオゾンを使用した場合には、テトラアルキルアンモニ
ウムの対イオンとして存在する炭酸イオン、炭酸水素イ
オン等によってオゾンの寿命は非常に短くなり、酸化剤
の分解工程を設ける必要はない。酸化処理の後に、先に
酸化処理をした場合と同様に逆浸透膜に加圧供給するこ
とによって廃液から水分を分離するが、逆浸透膜の性能
劣化を引き起こす有機物、酸化剤は既に分解されてお
り、また目詰まりを起こす析出微粒子も存在しないの
で、長期にわたり効率的な濃縮が行われる。On the other hand, the tetraalkylammonium hydroxide-containing waste liquid may be subjected to a neutralization treatment before the oxidation treatment. In this case, fine particles of a polymer substance such as a photoresist and a photosensitizer are deposited, but the deposit is disappeared by lowering the molecular weight of the polymer substance or decomposing the organic substance by subsequent oxidation treatment. Carbon dioxide,
Acids such as sulfuric acid and hydrochloric acid can be used, but carbon dioxide is preferably used. At the time of the oxidation treatment, it is necessary to decompose the oxidant so that the oxidant does not remain, but when carbon dioxide is used for neutralization and ozone is used as the oxidant, tetraalkylammonium The lifetime of ozone is extremely shortened by carbonate ions, hydrogen carbonate ions, etc. existing as counter ions, and it is not necessary to provide a step of decomposing the oxidant. After the oxidation treatment, water is separated from the waste liquid by supplying pressure to the reverse osmosis membrane in the same manner as in the case of performing the oxidation treatment earlier, but the organic substances and the oxidant that cause the performance deterioration of the reverse osmosis membrane have already been decomposed. In addition, since there are no precipitated fine particles that cause clogging, efficient concentration can be performed for a long time.
【００１３】[0013]
【作用】フォトリソグラフィー工程においてフォトレジ
ストの現像液として使用された有機物を含有する水酸化
テトラアルキルアンモニウム含有廃液を、酸化処理によ
って有機物を低分子化あるいは分解するとともに中和処
理した後に逆浸透膜へ加圧供給したので、逆浸透膜が析
出物によって目詰まりを起こしたりあるいはアルカリに
よって劣化することもなく、安定した廃液の処理が可能
である。[Function] A tetraalkylammonium hydroxide-containing waste liquid containing an organic substance used as a developer for a photoresist in a photolithography process is subjected to an oxidation treatment to reduce the molecular weight of the organic substance or decompose the neutralized substance and then to a reverse osmosis membrane. Since it is supplied under pressure, the reverse osmosis membrane is not clogged with precipitates or deteriorated by alkali, and stable waste liquid treatment is possible.
【００１４】[0014]
【実施例】以下に本発明の実施例を示し本発明を説明す
る。 実施例１ （現像廃液作製工程）ノボラック系のポジ型のフォトレ
ジスト（ＯＦＰＲ−８００ 東京応化工業（株）製）５
０ｇを、内面をフッ素樹脂でライニングした１０リット
ル容器の底面に薄く塗布し、９０℃、１２０分間温風乾
燥機内でプリベークし、レジスト中のエチルセロソルブ
およびその他の揮発性有機溶媒を蒸発除去し、次いで、
低圧水銀ランプを使用し、６０秒間紫外線照射露光した
後、高純度の２．３８重量％の水酸化テトラメチルアン
モニウムを含有する現像液（ＮＭＤ−Ｗ 東京応化工業
（株）製）１２リットルを加えて溶解した。次いで、リ
ンス工程において混入する水分に相当する超純水４８リ
ットルを加えた。得られた液の水酸化テトラアルキルア
ンモニウムの濃度は０．４８重量％、ＣＯＤ（Ｍｎ）値
は９００ｐｐｍ、ｐＨ１３．７であった。 （酸化処理工程）次いで、上記の工程で作製した現像廃
液に７０，０００ｐｐｍのオゾン含有気体に２リットル
／分の速度で、３０分間注入したところ現像廃液の色
は、オゾン注入前の暗褐色から薄い褐色となり、ＣＯＤ
（Ｍｎ）値は、８００ｐｐｍになった。またオゾン含有
気体の注入停止１５分後には残留オゾンは検出されなか
った。 （中和工程）酸化処理後の現像廃液に二酸化炭素を注入
し、ｐＨ７．２に中和したが、沈殿物の析出や浮遊微粒
子の存在は認められず、現像廃液の色には変化はなかっ
た。 （逆浸透膜による処理工程）中和処理後の現像廃液を、
逆浸透膜（ＳＵ−８１０ 東レ（株））を用いて現像廃
液の容量が３リットルとなるまで加圧供給し、２０倍に
濃縮した。濃縮した廃液中の炭酸テトラメチルアンモニ
ウムの濃度は約１０重量％であり、加圧ポンプ圧力は５
５ｋｇｆ／ｃｍ2 の条件で、透過水速度は１３リットル
／ｍ2 ・時であった。また、逆浸透膜によるテトラメチ
ルアンモニウム塩の阻止率は９９．９％と安定してお
り、逆浸透膜への悪影響は認められず、効率よく濃縮を
行うことができた。EXAMPLES The present invention will be described below by showing Examples of the present invention. Example 1 (Development waste liquid preparation step) Novolak-based positive photoresist (OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd.) 5
0 g was thinly applied to the bottom of a 10 liter container whose inner surface was lined with a fluororesin, prebaked at 90 ° C. for 120 minutes in a hot air drier to remove ethyl cellosolve and other volatile organic solvents in the resist by evaporation, Then
After exposure to ultraviolet irradiation for 60 seconds using a low-pressure mercury lamp, 12 liters of a developing solution (NMD-W manufactured by Tokyo Ohka Kogyo Co., Ltd.) containing high-purity 2.38 wt% tetramethylammonium hydroxide was added. Dissolved. Next, 48 liters of ultrapure water corresponding to the water content mixed in in the rinse step was added. The concentration of tetraalkylammonium hydroxide in the obtained liquid was 0.48% by weight, the COD (Mn) value was 900 ppm, and the pH was 13.7. (Oxidation treatment step) Next, when the developer waste solution produced in the above step was injected into the ozone-containing gas of 70,000 ppm at a rate of 2 liter / minute for 30 minutes, the color of the developer waste solution changed from dark brown before ozone injection. Light brown, COD
The (Mn) value was 800 ppm. Residual ozone was not detected 15 minutes after the injection of the ozone-containing gas was stopped. (Neutralization step) Carbon dioxide was injected into the developer waste solution after the oxidation treatment to neutralize it to pH 7.2, but no precipitation or the presence of suspended fine particles was observed, and the color of the developer waste solution did not change. It was (Treatment process by reverse osmosis membrane)
Using a reverse osmosis membrane (SU-810 Toray Co., Ltd.), the developer waste solution was supplied under pressure until the volume became 3 liters, and concentrated 20 times. The concentration of tetramethylammonium carbonate in the concentrated waste liquid is about 10% by weight, and the pressure of the pressurizing pump is 5%.
Under the condition of 5 kgf / cm 2 , the permeation rate was 13 liter / m 2 · hour. Further, the inhibition rate of the tetramethylammonium salt by the reverse osmosis membrane was stable at 99.9%, no adverse effect on the reverse osmosis membrane was observed, and the concentration could be performed efficiently.
【００１５】実施例２ 半導体装置の製造工程において、フォトレジストの現像
に使用された水酸化テトラメチルアンモニウムを０．２
重量％含有し、ＣＯＤ（Ｍｎ）値２０ｐｐｍ、ｐＨ１
２．５の現像廃液を原料とした。現像廃液の色は薄黄色
澄明であった。 （中和工程）現像廃液１ｍ3 に二酸化炭素を注入し、ｐ
Ｈ７．２に中和したところ、フォトレジスト等の微粒子
が析出し、現像廃液の色は薄黄色でやや不澄明となっ
た。 （酸化処理工程）次いで、７０，０００ｐｐｍのオゾン
含有気体を８リットル／分の速度で、１時間３０分注入
したところ、現像廃液の色は、薄黄色澄明でありＣＯＤ
（Ｍｎ）値６ｐｐｍであり、オゾン含有気体の注入停止
後１５分後には残留オゾンは検出されなかった。 （逆浸透膜による処理工程）中和処理と酸化処理を行っ
た現像廃液を、逆浸透膜（ＳＵ−８１０ 東レ（株））
を用いて現像廃液の容量が２０リットルとなるまで加圧
供給し、５０倍に濃縮した。濃縮した廃液中の炭酸テト
ラメチルアンモニウムの濃度は約１０重量％であり、加
圧ポンプ圧力は５５ｋｇｆ／ｃｍ2 の条件で、透過水速
度は１４リットル／ｍ2 ・時であった。また、逆浸透膜
によるテトラメチルアンモニウム塩の阻止率は９９．９
％と安定しており、透過水のＣＯＤ（Ｍｎ）値は１０ｐ
ｐｍ以下であり、逆浸透膜への悪影響は認められず、効
率よく濃縮を行うことができた。Example 2 In the process of manufacturing a semiconductor device, 0.2% tetramethylammonium hydroxide used for developing a photoresist is used.
% By weight, COD (Mn) value 20ppm, pH 1
The developing waste solution of 2.5 was used as a raw material. The color of the developing waste liquid was light yellow and clear. (Neutralization step) Carbon dioxide is injected into 1 m 3 of the developing waste liquid, and p
Upon neutralization with H7.2, fine particles such as photoresist were deposited, and the color of the waste developer was pale yellow and slightly unclear. (Oxidation treatment step) Next, when an ozone-containing gas of 70,000 ppm was injected at a rate of 8 liters / minute for 1 hour and 30 minutes, the color of the developing waste liquid was pale yellow and clear.
The (Mn) value was 6 ppm, and residual ozone was not detected 15 minutes after the injection of the ozone-containing gas was stopped. (Treatment process by reverse osmosis membrane) The development waste liquid subjected to the neutralization treatment and the oxidation treatment is treated with a reverse osmosis membrane (SU-810 Toray Co., Ltd.).
Was supplied under pressure until the volume of the developing waste liquid reached 20 liters, and concentrated 50 times. The concentration of tetramethylammonium carbonate in the concentrated waste liquid was about 10% by weight, the pressure of the pressurizing pump was 55 kgf / cm 2 , and the permeation rate was 14 liters / m 2 · hour. Further, the blocking rate of the tetramethylammonium salt by the reverse osmosis membrane is 99.9.
%, The COD (Mn) value of permeate is 10 p
Since it was pm or less, no adverse effect on the reverse osmosis membrane was observed, and the concentration could be performed efficiently.
【００１６】実施例３ 半導体装置の製造工程でのフォトリソグラフィーにおい
て、フォトレジストの現像に使用された水酸化テトラメ
チルアンモニウムを０．２重量％含有し、ＣＯＤ（Ｍ
ｎ）値は２０ｐｐｍ、ｐＨ１２．５の現像廃液を原料と
した。 （酸化処理および中和工程）現像廃液１ｍ3 を第１の気
液混合装置（カルマン・コンタック 冷化工業製）に、
２０リットル／分の流量で供給し、７０，０００ｐｐｍ
のオゾン含有気体を８リットル／分の速度で注入して反
応させ、次いで第２の気液混合装置に二酸化炭素を注入
し、ｐＨ７．２に中和した。溶液の色はオゾン注入前後
ともに薄黄色澄明であった。ＣＯＤ（Ｍｎ）値は１０ｐ
ｐｍであり、残留オゾンは検出されず、フォトレジスト
等の微粒子の析出も認められなかった。 （逆浸透膜による処理工程）次いで、現像廃液１ｍ3 を
逆浸透膜（ＳＵ−８１０ 東レ（株））を用いて現像廃
液の容量が２０リットルとなるまで加圧供給し、５０倍
に濃縮した。濃縮した廃液中の炭酸テトラメチルアンモ
ニウムの濃度は約１０重量％であり、加圧ポンプ圧力は
５５ｋｇｆ／ｃｍ2 の条件で、透過水速度は１４リット
ル／ｍ2 ・時であった。また、逆浸透膜によるテトラメ
チルアンモニウム塩の阻止率は９９．９％と安定してお
り、透過水のＣＯＤ（Ｍｎ）値は１０ｐｐｍ以下であ
り、逆浸透膜への悪影響は認められず、効率よく濃縮を
行うことができた。Example 3 In photolithography in the manufacturing process of a semiconductor device, 0.2% by weight of tetramethylammonium hydroxide used for developing a photoresist is contained and COD (M
n) value was 20 ppm, and a developing waste liquid having a pH of 12.5 was used as a raw material. (Oxidation and Neutralization Step) 1 m 3 of developing waste liquid was placed in a first gas-liquid mixing device (Kalman Contac Refrigeration Industry).
Supply at a flow rate of 20 liters / min, 70,000 ppm
The ozone-containing gas of 1. was injected at a rate of 8 l / min for reaction, and then carbon dioxide was injected into the second gas-liquid mixing device to neutralize the pH to 7.2. The color of the solution was light yellow and clear before and after ozone injection. COD (Mn) value is 10p
pm, no residual ozone was detected, and no precipitation of fine particles such as photoresist was observed. (Treatment Step Using Reverse Osmosis Membrane) Next, 1 m 3 of the development waste liquid was pressure-supplied using a reverse osmosis membrane (SU-810 Toray Co., Ltd.) until the volume of the development waste liquid reached 20 liters, and concentrated 50 times. . The concentration of tetramethylammonium carbonate in the concentrated waste liquid was about 10% by weight, the pressure of the pressurizing pump was 55 kgf / cm 2 , and the permeation rate was 14 liters / m 2 · hour. In addition, the rate of tetramethylammonium salt rejection by the reverse osmosis membrane was stable at 99.9%, the COD (Mn) value of the permeate was 10 ppm or less, and no adverse effect on the reverse osmosis membrane was observed. The concentration was good.
【００１７】比較例１ 実施例１で作製した現像廃液をオゾンによって酸化処理
をしないで、二酸化炭素を注入したところ、ｐＨ１１．
３付近から浮遊微粒子の存在が認められはじめ、ｐＨ１
０付近で析出が顕著となった。析出した微粒子を電子顕
微鏡で観察したところ、直径０．１〜１００μｍ程度の
広い範囲に分布が認められた。Comparative Example 1 When the developing waste liquid prepared in Example 1 was injected with carbon dioxide without being oxidized by ozone, the pH value was 11.
Presence of suspended fine particles began to be recognized from around 3, pH 1
Precipitation became remarkable around 0. When the deposited fine particles were observed with an electron microscope, a distribution was recognized in a wide range of a diameter of about 0.1 to 100 μm.
【００１８】比較例２ 実施例２において、中和処理した現像廃液を孔径０．１
μｍのホロファイバー型の外圧方式精密濾過膜（クラレ
製）にて濾過し、析出物を捕集したところ、ｐＨ７．２
の時点で５０ｐｐｍの析出物が認められ、また精密濾過
膜の透過速度は初期は１９０リットル／ｍ2 ・時から短
時間に１２リットル／ｍ2 ・時に低下し、逆洗を施して
も一時的に２０リットル／ｍ2 ・時程度に向上するのみ
であり、著しい目詰まりを示し、精密濾過によって析出
物を分離する方法は適当ではない。Comparative Example 2 In Example 2, the neutralization-treated developing waste liquid was treated with a pore size of 0.1.
When the precipitate was collected by filtration through a μm hollow fiber type external pressure type microfiltration membrane (manufactured by Kuraray), the pH was 7.2.
At the point of time, 50 ppm of precipitate was observed, and the permeation rate of the microfiltration membrane initially decreased from 190 liters / m 2 · hr to 12 liters / m 2 · hr in a short time, and even if backwashing was performed temporarily. in it is only improved to approximately at 20 l / m 2 ·, showed significant clogging, not suitable method for separating the precipitate by microfiltration.
【００１９】[0019]
【発明の効果】本発明は、水酸化テトラアルキルアンモ
ニウム含有廃液を酸化処理工程において含有している有
機物を酸化して低分子化あるいは分解をしたので、廃液
を中和処理しても高分子物質等が析出せず、もしくは中
和処理後に析出物を酸化分解処理することにより再度可
溶化処理することにより、濾過膜による処理を行わなく
ても逆浸透膜に目詰まりを起こすこともなく、安定した
廃液処理が可能である。INDUSTRIAL APPLICABILITY According to the present invention, since organic substances contained in the tetraalkylammonium hydroxide-containing waste liquid in the oxidation treatment step are oxidized to lower the molecular weight or decomposed, even if the waste liquid is neutralized, a high molecular substance is obtained. Etc. does not precipitate, or the precipitate is subjected to oxidative decomposition treatment after neutralization treatment to solubilize it again, so that the reverse osmosis membrane does not become clogged even without treatment with a filtration membrane, and is stable. Waste liquid treatment is possible.
【図１】本発明の方法を説明する図である。FIG. 1 is a diagram illustrating a method of the present invention.
１…廃液貯槽、２…酸化剤発生装置、３…酸貯槽、４…
ポンプ、５…酸化処理装置、６…中和処理装置、７…逆
浸透循環貯槽、８…高圧ポンプ、９…逆浸透膜、１０…
透過水1 ... Waste liquid storage tank, 2 ... Oxidizing agent generator, 3 ... Acid storage tank, 4 ...
Pump, 5 ... Oxidation treatment device, 6 ... Neutralization treatment device, 7 ... Reverse osmosis circulation storage tank, 8 ... High pressure pump, 9 ... Reverse osmosis membrane, 10 ...
Permeate
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０２Ｆ 1/66 Ｈ 1/78 ＺＡＢ 9/00 ５０２ Ｆ 7446−4Ｄ Ｒ 7446−4Ｄ ５０３ Ｃ 7446−4Ｄ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication C02F 1/66 H 1/78 ZAB 9/00 502 F 7446-4D R 7446-4D 503 C 7446- 4D
Claims (2)
廃液の処理方法において、該廃液中の有機物を酸化処理
によって低分子化あるいは分解するとともにｐＨ６〜８
に中和処理した後に、逆浸透膜に加圧供給して廃液中の
水分を分離することを特徴とする水酸化テトラアルキル
アンモニウム含有廃液の処理方法。1. A method for treating a tetraalkylammonium hydroxide-containing waste liquid, wherein an organic substance in the waste liquid is reduced in molecular weight or decomposed by an oxidation treatment and has a pH of 6 to 8.
A method for treating a tetraalkylammonium hydroxide-containing waste liquid, characterized in that the water in the waste liquid is separated by pressurizing and supplying to a reverse osmosis membrane after neutralizing the waste liquid.
に、中和処理を二酸化炭素の注入によって行うことを特
徴とする請求項１記載の水酸化テトラアルキルアンモニ
ウム含有廃液の処理方法。2. The method for treating a tetraalkylammonium hydroxide-containing waste liquid according to claim 1, wherein the oxidation treatment is performed by ozone and the neutralization treatment is performed by injecting carbon dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28509993A JP3392483B2 (en) | 1993-11-15 | 1993-11-15 | Treatment method for wastewater containing tetraalkylammonium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28509993A JP3392483B2 (en) | 1993-11-15 | 1993-11-15 | Treatment method for wastewater containing tetraalkylammonium hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07136651A true JPH07136651A (en) | 1995-05-30 |
| JP3392483B2 JP3392483B2 (en) | 2003-03-31 |
Family
ID=17687117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28509993A Expired - Fee Related JP3392483B2 (en) | 1993-11-15 | 1993-11-15 | Treatment method for wastewater containing tetraalkylammonium hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3392483B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997023415A1 (en) * | 1995-12-22 | 1997-07-03 | Henkel-Ecolab Gmbh & Co. Ohg | Treatment of alkaline rinse water by reverse osmosis following neutralisation with biogenic carbon dioxide |
| KR100361799B1 (en) * | 1998-01-05 | 2003-02-05 | 오르가노 코포레이션 | Method and apparatus for regenerating photoresist developing waste liquid |
| WO2008056671A1 (en) * | 2006-11-09 | 2008-05-15 | Tokuyama Corporation | Method of neutralizing developer waste liquid containing tetraalkylammonium hydroxide |
-
1993
- 1993-11-15 JP JP28509993A patent/JP3392483B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997023415A1 (en) * | 1995-12-22 | 1997-07-03 | Henkel-Ecolab Gmbh & Co. Ohg | Treatment of alkaline rinse water by reverse osmosis following neutralisation with biogenic carbon dioxide |
| KR100361799B1 (en) * | 1998-01-05 | 2003-02-05 | 오르가노 코포레이션 | Method and apparatus for regenerating photoresist developing waste liquid |
| WO2008056671A1 (en) * | 2006-11-09 | 2008-05-15 | Tokuyama Corporation | Method of neutralizing developer waste liquid containing tetraalkylammonium hydroxide |
| JP5041297B2 (en) * | 2006-11-09 | 2012-10-03 | 株式会社トクヤマ | Method for neutralizing developer wastewater containing tetraalkylammonium hydroxide |
| TWI416278B (en) * | 2006-11-09 | 2013-11-21 | Tokuyama Corp | Neutralization method of developing waste liquid containing tetraalkylammonium hydroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3392483B2 (en) | 2003-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3491666B2 (en) | Method and apparatus for controlling TOC component removal | |
| KR101353002B1 (en) | Treating method and treating apparatus of waste water containing organic material and | |
| JP3360365B2 (en) | Method for regenerating tetraalkylammonium hydroxide | |
| US5354434A (en) | Method for regenerating tetraalkylammonium hydroxide | |
| KR101476864B1 (en) | Method and apparatus for removing organic matters | |
| US5523001A (en) | Treatment of electroless plating waste streams | |
| JP3109525B2 (en) | Method for regenerating tetraalkylammonium hydroxide | |
| JP3110513B2 (en) | Method for regenerating tetraalkylammonium hydroxide | |
| JP3392483B2 (en) | Treatment method for wastewater containing tetraalkylammonium hydroxide | |
| JP3506171B2 (en) | Method and apparatus for removing TOC component | |
| KR101360314B1 (en) | Method for treating waste water containing surfactant | |
| JPH1199394A (en) | Method for removing organic matter in water | |
| JP2001113291A (en) | Apparatus for treating organic matter-containing water | |
| JPH0517889A (en) | Method for regenerating tetra-alkyl ammonium hydroxide | |
| JPH10244280A (en) | Removal device for organic substance in water | |
| JPH10314763A (en) | Method for treatment of organic matter-containing waste liquid | |
| JPH11347591A (en) | Treatment of sewage containing biologically hardly decomposable organic matter | |
| JPS63294989A (en) | Treatment of photoresist-containing waste water | |
| JP2000263072A (en) | Method and apparatus for treating wastewater | |
| JP2003080274A (en) | Treatment method and equipment for sewage | |
| JPH0314518B2 (en) | ||
| JP2001054798A (en) | Method and apparatus for treating harmful material in sewage | |
| JPH11267692A (en) | Treatment of laundry waste liquid | |
| JP2007098244A (en) | Recycling method of ozone-containing drain | |
| JPH0679266A (en) | Method for removing cod of sewage leaching from refuse landfill |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080124 Year of fee payment: 5 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090124 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |