JPH08197094A - Semiconductor cleaning wastewater collection method - Google Patents
Semiconductor cleaning wastewater collection methodInfo
- Publication number
- JPH08197094A JPH08197094A JP7024507A JP2450795A JPH08197094A JP H08197094 A JPH08197094 A JP H08197094A JP 7024507 A JP7024507 A JP 7024507A JP 2450795 A JP2450795 A JP 2450795A JP H08197094 A JPH08197094 A JP H08197094A
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- anion exchange
- semiconductor cleaning
- cleaning wastewater
- water
- 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 Ion Exchange (AREA)
- Water Treatment By Sorption (AREA)
Abstract
(57)【要約】
【目的】半導体洗浄排水を生物処理した処理水を回収再
利用するための処理水中に残留する菌体の簡単な分離方
法を提供する。
【構成】半導体洗浄排水を生物処理した後、超純水製造
工程に供給するための半導体洗浄排水の回収方法におい
て、該半導体洗浄排水を生物反応槽で生物処理して生成
する処理水を、ＯＨ形陰イオン交換樹脂、好ましくは強
塩基性陰イオン交換樹脂と接触処理させることよりなる
半導体洗浄排水の回収方法。
(57) [Abstract] [Purpose] To provide a simple method for separating bacterial cells remaining in treated water to recover and reuse treated water obtained by biologically treating semiconductor cleaning wastewater. In a method for recovering semiconductor cleaning wastewater for supplying it to an ultrapure water production process after biologically treating the semiconductor cleaning wastewater, treated water produced by biologically treating the semiconductor cleaning wastewater in a biological reaction tank is OH. A method for recovering wastewater from semiconductor washing, which comprises contacting with a shaped anion exchange resin, preferably a strongly basic anion exchange resin.
Description
【０００１】[0001]
【産業上の利用分野】本発明は半導体製造工場から排出
される半導体洗浄排水の処理方法に関するものであり、
更に詳しくは、生物処理した半導体洗浄排水を超純水製
造用水として回収再使用するのに好適な半導体洗浄排水
の回収方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating semiconductor cleaning wastewater discharged from a semiconductor manufacturing plant,
More specifically, the present invention relates to a method for recovering semiconductor cleaning wastewater suitable for recovering and reusing biologically treated semiconductor cleaning wastewater as ultrapure water production water.
【０００２】[0002]
【従来の技術】半導体の製造工程では、超純水製造設備
で製造された多量の超純水が洗浄用水として使用されて
いる。使用された超純水は洗浄排水として排出される
が、最近では水事情の逼迫から、この洗浄排水を回収
し、再処理した後循環利用するための効率的方法が望ま
れている。この洗浄排水中には、半導体製造工程で使用
された２−プロパノールやアセトンなどの有機溶媒が有
機物として含まれているため、超純水の製造用水として
回収再使用するにあたっては、排水中のこれらの有機物
を除去することが必要である。2. Description of the Related Art In a semiconductor manufacturing process, a large amount of ultrapure water produced in an ultrapure water production facility is used as cleaning water. The ultrapure water used is discharged as cleaning wastewater, but recently, due to the tight water situation, an efficient method for collecting this cleaning wastewater, reprocessing it, and recycling it is desired. Since organic solvents such as 2-propanol and acetone used in the semiconductor manufacturing process are contained in this cleaning wastewater, when recovered and reused as water for production of ultrapure water, these wastewater in the wastewater are used. It is necessary to remove the organic matter.
【０００３】通常、半導体洗浄排水には有機物がＴＯＣ
として１〜５ｍｇ／Ｌ程度含まれており、この有機物の
除去手段としては生物処理方法が採用されている。生物
処理方法としては、処理水中への微生物の流出が比較的
少ない方法、例えば有機物を分解する微生物による生物
膜を担体上に形成担持した充填材を充填した生物反応槽
中で半導体洗浄排水を処理する方法などが採用されるこ
とが多い。しかし、このような処理方法においても充填
材より剥離した微量の微生物が処理水中に流出し、これ
らが超純水製造設備内で増殖してトラブルの原因となる
ことが避けられないため、生物反応槽で処理された処理
水は、一旦菌体分離器に導入して菌体等の微生物を除去
した後に超純水製造設備に循環再使用されている（特公
平６−４５０３６）。従来、この様な菌体分離方法とし
ては、精密濾過(MF)膜モジュールまたは限外濾過(UF)膜
モジュールなどの分離膜モジュールにより構成された菌
体分離器に生物反応槽からの処理水を通液して菌体分離
を行う方法が採用されている。Organic matter is usually contained in TOC in the semiconductor cleaning wastewater.
1 to 5 mg / L, and a biological treatment method is adopted as a means for removing the organic matter. As a biological treatment method, a method in which the outflow of microorganisms into the treated water is relatively small, for example, a semiconductor cleaning wastewater is treated in a biological reaction tank filled with a packing material in which a biofilm is formed on a carrier by a microorganism that decomposes organic substances. The method of doing is often adopted. However, even in such a treatment method, it is unavoidable that a small amount of microorganisms exfoliated from the filler will flow into the treated water, and these will proliferate in the ultrapure water production facility and cause troubles. The treated water treated in the tank is once introduced into a microbial cell separator to remove microorganisms such as microbial cells and then circulated and reused in an ultrapure water production facility (Japanese Patent Publication No. 6-45036). Conventionally, such a bacterial cell separation method has been performed by treating treated water from a biological reaction tank in a bacterial cell separator configured by a separation membrane module such as a microfiltration (MF) membrane module or an ultrafiltration (UF) membrane module. A method of separating cells by passing a liquid is adopted.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、従来の
分離膜を用いた菌体分離器において、生物反応槽より流
出する処理水から菌体を分離する半導体洗浄排水の回収
方法には、次のような問題点があった。すなわち、菌体
分離器では、精密濾過膜または限外濾過膜などの膜によ
って菌体を分離するので、装置内で増殖した菌体や菌体
が分泌する高分子有機物によって膜が閉塞し、通水流量
が安定して得られない欠点があった。そのため、菌体分
離器では、膜の閉塞を極力防止するために、水や空気に
よる頻繁な膜面洗浄が必須である。また、このような機
械的な洗浄のほかに、膜モジュール内に増殖した菌体を
殺菌するために、殺菌剤による殺菌操作を定期的に行わ
ねばならない。更に、膜を閉塞させている物質を溶解除
去するために、アルカリや界面活性剤などによる薬剤洗
浄も必要である。このように、従来の膜を用いた菌体分
離方法では、極めて煩雑な作業を要していた。However, in the conventional microbial cell separator using a separation membrane, the following is a method for recovering semiconductor washing wastewater for separating microbial cells from the treated water flowing out from the biological reaction tank as follows. There was a problem. That is, in the microbial cell separator, the microbial cells are separated by a membrane such as a microfiltration membrane or an ultrafiltration membrane. There was a drawback that the water flow rate was not stable. Therefore, in the bacterial cell separator, frequent cleaning of the membrane surface with water or air is essential in order to prevent the membrane from being blocked. In addition to such mechanical cleaning, a sterilizing operation with a bactericide must be regularly performed in order to sterilize the bacterial cells grown in the membrane module. Furthermore, in order to dissolve and remove the substance that clogs the membrane, it is necessary to wash the chemical with an alkali or a surfactant. As described above, the conventional method for separating bacterial cells using a membrane requires extremely complicated work.
【０００５】[0005]
【課題を解決するための手段】そこで、本発明者等は、
半導体洗浄排水を生物処理した処理水を回収再利用する
にあたり、処理水中に残留する菌体の簡単な分離方法に
ついて鋭意検討を行い、本発明に至った。すなわち、本
発明は、半導体洗浄排水を生物処理した後、超純水製造
工程に供給するための半導体洗浄排水の回収方法におい
て、該半導体洗浄排水を生物反応槽で生物処理して生成
する処理水を、ＯＨ形陰イオン交換樹脂と接触処理させ
ることよりなる半導体洗浄排水の回収方法及び該ＯＨ形
陰イオン交換樹脂として強塩基性であり、またその架橋
度が２〜１０％のゲル型の陰イオン交換樹脂を使用する
ことを要旨とするものである。Therefore, the present inventors have
In recovering and reusing the treated water obtained by biologically treating the semiconductor cleaning wastewater, the inventors of the present invention have made intensive studies on a simple method for separating bacterial cells remaining in the treated water, and have reached the present invention. That is, the present invention is a method for recovering semiconductor cleaning wastewater for biological treatment of semiconductor cleaning wastewater and then supplying it to the ultrapure water manufacturing process, wherein treated water produced by biologically treating the semiconductor cleaning wastewater in a biological reaction tank. A method for recovering semiconductor washing wastewater, which comprises contact-treating with an OH type anion exchange resin, and a gel type anion having a strong basicity as the OH type anion exchange resin and having a crosslinking degree of 2 to 10%. The gist is to use an ion exchange resin.
【０００６】本発明を図１に基づいてさらに具体的に説
明する。図１は本発明に係わる半導体洗浄排水の回収方
法の概略系統図の一例を示す。図中、超純水製造システ
ム（設備）それ自体は公知であり、原水の種類、製造さ
れた超純水の用途等に従って若干の違いはあるが、半導
体の製造分野では、一般に前処理システム（凝集沈澱、
濾過、殺菌剤注入等）、一次純水システム（膜濾過、脱
気処理、イオン交換等）、二次純水（サブ）システム
（イオン交換、膜濾過、紫外線酸化等）から構成され、
これに排水処理システム及び／又は排水回収システムが
付設されている。The present invention will be described more specifically with reference to FIG. FIG. 1 shows an example of a schematic system diagram of a semiconductor cleaning wastewater recovery method according to the present invention. In the figure, the ultrapure water production system (equipment) itself is known, and there are some differences depending on the type of raw water, the purpose of the produced ultrapure water, etc. Cohesive precipitation,
Filtration, sterilizer injection, etc.), primary pure water system (membrane filtration, degassing, ion exchange, etc.), secondary pure water (sub) system (ion exchange, membrane filtration, UV oxidation, etc.),
A wastewater treatment system and / or a wastewater recovery system is attached to this.
【０００７】超純水製造システムで製造された超純水は
半導体製造工程に供給され、半導体の洗浄に供される。
洗浄後に排出される半導体洗浄排水は、生物処理装置に
導入して該排水中に含まれている有機物を分解する。生
物処理装置としては、菌体の流出が比較的少ない生物反
応槽方式の採用が主流となるが、この生物反応槽には、
有機物を分解する菌体による生物膜を担体上に形成担持
した粒状又は繊維状の充填材が装填されている。菌体を
担持する担体としては、たとえば粒状又は繊維状活性
炭、濾過砂、珪藻土などが使用されるが、粒状又は繊維
状活性炭が好ましい。生物反応槽での反応方式として
は、固定層或いは流動層方式のいずれでも良いが、一般
には固定層方式が採用される。また、生物反応槽への通
水は、上向流、下向流、水平流のいずれでもよい。The ultrapure water produced by the ultrapure water production system is supplied to the semiconductor production process and used for cleaning the semiconductor.
The semiconductor cleaning wastewater discharged after cleaning is introduced into a biological treatment apparatus to decompose organic substances contained in the wastewater. As a biological treatment device, the mainstream is the adoption of a biological reaction tank system in which the outflow of cells is relatively small.
It is loaded with a granular or fibrous filler in which a biofilm formed by cells that decompose organic matter is formed and supported on a carrier. As the carrier for supporting the bacterial cells, for example, granular or fibrous activated carbon, filter sand, diatomaceous earth, etc. are used, but granular or fibrous activated carbon is preferable. The reaction system in the biological reaction vessel may be either a fixed bed or fluidized bed system, but a fixed bed system is generally adopted. The water flow to the biological reaction tank may be any of upward flow, downward flow, and horizontal flow.
【０００８】微生物膜を担体上に形成担持させる方法と
しては、微生物固定化の公知方法を採用することが出
来、例えば、予め培養した当該排水中の有機物を効率良
く分解する菌体を、必要に応じ栄養塩とともに当該排水
に添加し、これを担体の充填層に循環通水し、担体表面
に菌体を固定化し、微生物膜を形成させることが出来
る。生物処理の際、菌体の増殖による有機物の分解に必
要な栄養塩が排水中に不足している場合には、該排水に
栄養塩を添加し、混合した後に、これを生物処理装置に
導入する。添加される栄養塩は、有機物の量に応じ、そ
の有機物の炭素を資化するのに必要な量加えればよく、
通常塩化アンモニウム、硫酸アンモニウム等のアンモニ
ウム塩、リン酸水素カリウム、リン酸水素ナトリウム等
のリン酸塩が用いられ、ＢＯＤ：Ｎ：Ｐ＝100：5：1程
度の割合で添加するのが好ましい。また、有機物の分解
に必要な溶存酸素が不足する場合には、酸素を補給する
ために、生物処理装置の処理水の一部を分岐し、これを
空気曝気した後に生物処理装置に供給する。As a method for forming and supporting a microbial membrane on a carrier, a known method for immobilizing microorganisms can be adopted. For example, bacterial cells which efficiently decompose organic matter in the waste water pre-cultured are required. It is possible to add a nutrient salt to the drainage and to circulate it through the packed bed of the carrier to immobilize the bacterial cells on the surface of the carrier to form a microbial membrane. When the wastewater lacks the nutrient salts required for the decomposition of organic substances due to the growth of bacterial cells during biological treatment, the nutrient salts are added to the wastewater, mixed, and then introduced into the biological treatment apparatus. To do. The nutrient salt to be added may be added in an amount necessary to assimilate the carbon of the organic matter according to the amount of the organic matter,
Usually, ammonium salts such as ammonium chloride and ammonium sulfate, and phosphates such as potassium hydrogenphosphate and sodium hydrogenphosphate are used, and it is preferable to add them at a ratio of about BOD: N: P = 100: 5: 1. Further, when the dissolved oxygen necessary for decomposing the organic matter is insufficient, a part of the treated water of the biological treatment device is branched to supplement the oxygen, and this is aerated and then supplied to the biological treatment device.
【０００９】本発明方法では生物処理装置から流出する
処理水は、ＯＨ形陰イオン交換樹脂によって接触処理さ
れ、処理水に同伴する菌体が吸着除去される。ＯＨ形陰
イオン交換樹脂としては、強塩基性陰イオン交換樹脂あ
るいは弱塩基性陰イオン交換樹脂であっても菌体の除去
はできるが、ＯＨ形強塩基性陰イオン交換樹脂を用いる
と一層良く菌体を除去できる。ＯＨ形陰イオン交換樹脂
として使用する陰イオン交換樹脂は、架橋度２〜１０％
のゲル型のＯＨ形強塩基性陰イオン交換樹脂、例えば、
三菱化学(株)製：商品名ダイヤイオンＳＡ１０Ａ、ＳＴ
Ａ１０等が適しているが、望ましくは架橋度２〜８％、
更に望ましくは２〜５％のゲル型のＯＨ形強塩基性陰イ
オン交換樹脂を用いるのがよい。また、強塩基性陰イオ
ン交換樹脂はＩ型でもII型でも使用できるが、II型より
やや化学的安定性が高いＩ型が好ましい。In the method of the present invention, the treated water flowing out of the biological treatment apparatus is contact-treated with an OH-type anion exchange resin to adsorb and remove the bacterial cells accompanying the treated water. As the OH type anion exchange resin, even if it is a strong basic anion exchange resin or a weak basic anion exchange resin, the bacterial cells can be removed, but it is better to use the OH type strong basic anion exchange resin. The cells can be removed. The anion exchange resin used as the OH type anion exchange resin has a crosslinking degree of 2 to 10%.
Gel type OH type strong basic anion exchange resin, for example,
Mitsubishi Chemical Co., Ltd .: Trade name Diaion SA10A, ST
A10 and the like are suitable, but the degree of crosslinking is preferably 2 to 8%,
It is more preferable to use a gel type OH type strong basic anion exchange resin of 2 to 5%. The strongly basic anion exchange resin can be used in either type I or type II, but type I, which has a slightly higher chemical stability than type II, is preferred.
【００１０】陰イオン交換樹脂との接触処理は、実際に
は生物処理装置から流出する生物処理水をＯＨ形強塩基
性イオン交換樹脂を充填した充填塔に通水することによ
り接触処理される。その際、処理水は通常、通水線速度
３〜６０ｍ／ｈ、空間速度３〜５０(L／h)Ｌー樹脂の条
件で下向流に通水される。本発明方法において生物処理
された処理水に含まれる菌体がＯＨ形の陰イオン交換樹
脂により吸着、除去されるのは、処理水中の菌体が負の
ゼータ電位を有するため、正のゼータ電位を有する陰イ
オン交換樹脂にクーロン力によって付着するメカニズム
によるものと考えられる。The contact treatment with the anion exchange resin is actually carried out by passing biologically treated water flowing out of the biological treatment apparatus through a packed column filled with an OH type strongly basic ion exchange resin. At that time, the treated water is normally passed in a downward flow under the conditions of a linear water velocity of 3 to 60 m / h and a space velocity of 3 to 50 (L / h) L-resin. In the method of the present invention, the cells contained in the treated water that has been biologically treated are adsorbed and removed by the OH-type anion exchange resin because the cells in the treated water have a negative zeta potential. It is believed that this is due to the mechanism of attachment to the anion exchange resin having a coulomb force.
【００１１】ＯＨ形陰イオン交換樹脂塔から流出する処
理水中への菌体のリークの監視は、樹脂塔の処理水の出
口付近に菌体を検出できる感度を有する微粒子計を設置
することにより行い、処理水中にリークする微粒子数が
所定の値に達した時点で通水を停止して、該イオン交換
樹脂の再生処理を実施する。ここで採用する微粒子計と
しては、ＯＨ形陰イオン交換樹脂床から流出する処理水
中の菌種の寸法に応じて適切な検出感度を有する微粒子
計を選定すれば良く、特に制限されるものではない。た
とえば、ＯＨ形陰イオン交換樹脂床から流出する処理水
中に同伴流出する菌種は、通常、直径０．２〜０．３μ
ｍ、長さ１μｍ程度のシュードモナス菌が主体であるた
め、粒径０．２μｍ以上の微粒子を検出できる微粒子計
を採用すれば良い。超純水を製造するための用水として
は、その超純水製造工程の循環する場所によっても異な
るが、通常、イオン交換塔からの処理水中の微粒子数は
多くとも１００個／ｍｌ以下であることが望ましい。Leakage of bacterial cells into the treated water flowing out from the OH type anion exchange resin tower is monitored by installing a fine particle meter having a sensitivity capable of detecting bacterial cells near the outlet of the treated water of the resin tower. The water flow is stopped when the number of fine particles leaking into the treated water reaches a predetermined value, and the ion exchange resin is regenerated. As the fine particle meter used here, a fine particle meter having appropriate detection sensitivity may be selected according to the size of the bacterial species in the treated water flowing out from the OH type anion exchange resin bed, and is not particularly limited. . For example, the bacterial species that accompany and flow out into the treated water flowing out from the OH type anion exchange resin bed usually has a diameter of 0.2 to 0.3 μm.
Since Pseudomonas bacteria having a size of m and a length of about 1 μm are mainly used, a fine particle meter capable of detecting fine particles having a particle diameter of 0.2 μm or more may be employed. Water used for producing ultrapure water varies depending on the circulating place of the ultrapure water production process, but normally the number of fine particles in the treated water from the ion exchange tower is 100 particles / ml or less at most. Is desirable.
【００１２】菌体の吸着能力が低下した陰イオン交換樹
脂の再生処理は、通常の再生方法が適用され、例えばア
ルカリ水溶液（４％苛性ソーダ水溶液、液温４０〜５０
℃）により再生処理を行なう。再生処理は陰イオン交換
樹脂塔の中で実施しても、陰イオン交換樹脂を外部に取
り出して別途再生処理しても良い。再生処理が終了した
後、再びこの陰イオン交換樹脂は生物処理水の処理のた
めに供される。陰イオン交換樹脂に吸着された菌体が再
生処理で脱離されるのは、再生液の苛性ソーダ水溶液に
さらされた樹脂層内がアルカリ性となり、菌体の負のゼ
ータ電位の絶対値と陰イオン交換樹脂の正のゼータ電位
の絶対値とがともに小さくなり、菌体と陰イオン交換樹
脂との間の静電的な吸引力が消失するためと考えられ
る。The regeneration treatment of the anion exchange resin having a reduced ability to adsorb the cells is carried out by a conventional regeneration method, for example, an alkaline aqueous solution (4% caustic soda aqueous solution, liquid temperature 40-50).
Regeneration treatment is performed at (° C). The regeneration treatment may be carried out in the anion exchange resin tower, or the anion exchange resin may be taken out and regenerated separately. After the regeneration treatment is completed, the anion exchange resin is again used for treatment of biological treated water. The cells adsorbed on the anion-exchange resin are desorbed during the regeneration process because the resin layer exposed to the aqueous solution of caustic soda in the regenerant becomes alkaline and the negative zeta potential of the cells and the anion exchange It is considered that this is because both the absolute value of the positive zeta potential of the resin becomes smaller and the electrostatic attraction between the bacterial cells and the anion exchange resin disappears.
【００１３】なお、ＯＨ形陰イオン交換樹脂床で処理す
る前の生物処理水中に、半導体洗浄排水或いは生物反応
槽に添加された栄養塩に由来するアンモニウムイオン等
の陽イオンが含まれる場合には、ＯＨ形陰イオン交換樹
脂、例えば、三菱化学(株)製：商品名ダイヤイオンＳＡ
１０ＡとＨ形陽イオン交換樹脂、例えば、三菱化学(株)
製：ダイヤイオンＳＫ１１０とを混合して通水する混床
式イオン交換樹脂床を用いたり、Ｈ形陽イオン交換樹脂
塔をＯＨ形陰イオン交換樹脂塔の前に設けてこれらを順
に通水する方法を用いれば、陽イオンが除去され、しか
も菌体も効率よく除去することができる。この場合、Ｈ
形陽イオン交換樹脂としてはゲル型の強酸性陽イオン交
換樹脂、例えば、ダイヤイオンＳＫ１１０、弱酸性陽イ
オン交換樹脂、例えば、三菱化学(株)製：商品名ダイヤ
イオンＷＫ２０を使用できるが、強酸性陽イオン交換樹
脂が有利である。When cations such as ammonium ions derived from the semiconductor washing wastewater or the nutrient salts added to the biological reaction tank are contained in the biologically treated water before being treated with the OH type anion exchange resin bed, , OH type anion exchange resin, for example, manufactured by Mitsubishi Chemical Corporation: trade name Diaion SA
10A and H type cation exchange resin, for example, Mitsubishi Chemical Corporation
Manufactured: A mixed-bed type ion exchange resin bed that mixes with Diaion SK110 to pass water is used, or an H type cation exchange resin tower is installed in front of the OH type anion exchange resin tower to pass water in order. By using the method, cations can be removed, and bacterial cells can be efficiently removed. In this case, H
As the form cation exchange resin, a gel type strong acid cation exchange resin, for example, Diaion SK110, a weak acid cation exchange resin, for example, Mitsubishi Kagaku Co., Ltd .: trade name Diaion WK20 can be used. Cation exchange resins are preferred.
【００１４】陰イオン交換樹脂で処理して得られた処理
水は、ＴＯＣが殆ど除去され高純度であるので、そのま
ま超純水製造システムに循環することができるが、必要
に応じ更に逆浸透膜、限外濾過膜等の膜分離処理を施し
てもよい。処理水を循環する場合、通常、陰イオン交換
樹脂塔は生物反応槽に付設されることが多いので、生物
反応槽の設置される場所によって超純水製造システムに
循環する場所も異なり、例えば前処理システムの原水入
口、又は前処理システムと一次純水システムの間等に処
理水を循環することができる。The treated water obtained by treating with an anion exchange resin can be circulated to the ultrapure water production system as it is because TOC is almost removed and it is of high purity. Alternatively, a membrane separation treatment such as an ultrafiltration membrane may be performed. When the treated water is circulated, the anion exchange resin tower is usually attached to the biological reaction tank, so the location where the biological reaction tank is circulated also differs depending on the location where the biological reaction tank is installed. The treated water can be circulated, such as at the raw water inlet of the treatment system or between the pretreatment system and the primary pure water system.
【００１５】[0015]
【実施例】次に、本発明を実施例及び比較例によりさら
に具体的に説明するが、本発明はその要旨を越えない限
り以下の実施例に限定されるものではない。EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.
【００１６】実施例 図２に従い、半導体洗浄排水を生物処理した後、その処
理水をＯＨ形陰イオン交換樹脂塔に通水し、菌体の除去
テストを行った。まず、半導体洗浄排水を、容量２００
０Ｌの塩化ビニル樹脂製の被処理水槽に供給し貯槽す
る。水温２０〜２５℃の半導体洗浄排水は、被処理水槽
から塩化ビニル樹脂製のポンプにより、流量５４Ｌ／ｈ
の割合で生物反応槽に供給する。生物反応槽は、塩化ビ
ニル樹脂製の直径２００ｍｍ、高さ１５００ｍｍの円筒
であり、筒内に層高９７０ｍｍに３０Ｌの粒状活性炭
（三菱化学（株）製：商品名ダイヤホープ００６Ｎ）を
充填し、この充填層にあらかじめ半導体洗浄排水を約１
ケ月間通水して充填材の活性炭表面にシュードモナス菌
を主体とする生物膜を形成させたものを菌体として使用
した。Example According to FIG. 2, the semiconductor cleaning wastewater was biologically treated, and then the treated water was passed through an OH type anion exchange resin tower to carry out a bacterial cell removal test. First, the semiconductor cleaning drainage is 200
It is supplied to and stored in a 0 L vinyl chloride resin treated water tank. The semiconductor cleaning wastewater with a water temperature of 20 to 25 ° C. has a flow rate of 54 L / h from the water tank to be treated by a vinyl chloride resin pump.
Is supplied to the bioreactor at a rate of. The biological reaction tank is a cylinder made of vinyl chloride resin having a diameter of 200 mm and a height of 1500 mm, and 30 L of granular activated carbon (manufactured by Mitsubishi Chemical Co., Ltd .: trade name Diamond Hope 006N) is filled in the cylinder with a layer height of 970 mm. Approximately 1 drainage of semiconductor cleaning water is added to this packed bed in advance.
Water was passed for a month to form a biofilm mainly composed of Pseudomonas bacteria on the surface of the activated carbon of the filler, which was used as a microbial cell.
【００１７】一方、生物反応槽には栄養塩槽から、塩化
ビニル樹脂製のポンプにより、栄養塩水溶液を流量６Ｌ
／ｈの割合で供給した。その際、栄養塩水溶液と被処理
水とを生物反応槽の入口配管内で混合し、この混合液を
生物反応槽に導入した。栄養塩水溶液は、栄養塩槽にお
いて、NH4Cl 200 μg-N/L、K2HPO4 80 μg-P/L、の２
種類の塩を超純水に所定の濃度に溶解して調製した。生
物反応槽は、通水量：６０Ｌ／ｈ、通水線速度：１．９
ｍ／ｈ、通水空間速度：２．０（Ｌ／ｈ）Ｌ−活性炭の
条件で操作した。生物反応槽から流出する生物処理液
は、ＯＨ形陰イオン交換樹脂塔に供給した。陰イオン交
換樹脂塔としては、アクリル樹脂製の直径１５０ｍｍ，
高さ１５００ｍｍの塔にＯＨ形強塩基性陰イオン交換樹
脂（三菱化学（株）製、商品名ダイヤイオンＳＡＴ１
０：ゲル型，Ｉ型、架橋度８％）１２Ｌを層高６８０ｍ
ｍに充填したものを使用した。On the other hand, in the biological reaction tank, a nutrient salt solution is supplied from a nutrient salt tank by a pump made of vinyl chloride resin to a flow rate of 6 L.
/ H was supplied. At that time, the nutrient salt aqueous solution and the water to be treated were mixed in the inlet pipe of the biological reaction tank, and this mixed solution was introduced into the biological reaction tank. In the nutrient salt tank, the aqueous solution of nutrient salt was prepared as follows: NH 4 Cl 200 μg-N / L, K 2 HPO 4 80 μg-P / L, 2
It was prepared by dissolving various kinds of salts in ultrapure water to a predetermined concentration. The biological reaction tank has a water flow rate of 60 L / h and a water flow linear velocity of 1.9.
m / h, water space velocity: 2.0 (L / h) It operated on the conditions of L- activated carbon. The biological treatment liquid flowing out from the biological reaction tank was supplied to the OH type anion exchange resin tower. As the anion exchange resin tower, a diameter of 150 mm made of acrylic resin,
OH type strong basic anion exchange resin (Mitsubishi Chemical Co., Ltd., trade name Diaion SAT1)
0: Gel type, I type, degree of crosslinking 8%) 12L layer height 680m
What was filled in m was used.
【００１８】陰イオン交換樹脂塔での処理操作は、通水
流量６０Ｌ／ｈ、通水線速度３．４ｍ／ｈ、通水空間速
度５．０（Ｌ／ｈ）Ｌ−樹脂で行った。陰イオン交換樹
脂塔の出口近くに微粒子計を設け、流出液中の微粒子数
を監視した。通水を開始してから４８時間後に１００個
／ｍｌとなったので、その時点で、陰イオン交換樹脂塔
への通水を中断し、イオン交換樹脂を常法により、４％
ＮａＯＨ水溶液２９Ｌ／回を用いて再生を行った。再生
後の樹脂塔に再び生物処理水を通液し、その操作を繰り
返し実施した。The treatment operation in the anion exchange resin tower was carried out at a water flow rate of 60 L / h, a water flow linear velocity of 3.4 m / h, and a water flow space velocity of 5.0 (L / h) L-resin. A particle counter was installed near the outlet of the anion exchange resin tower to monitor the number of particles in the effluent. After 48 hours from the start of water flow, the number reached 100 / ml, so at that point, the water flow to the anion exchange resin tower was stopped and the ion exchange resin was changed to 4% by the conventional method.
Regeneration was carried out using 29 L / aqueous NaOH solution. The biologically treated water was again passed through the resin tower after the regeneration, and the operation was repeated.
【００１９】処理結果を第１表に示す。なお、ＭＦ値
は、試料水1.0 Ｌ を孔径0.45μｍ、直径47mmのメンブ
レンフィルタによって-67 kPaの圧力で吸引濾過するの
に要する時間（秒）である。濾過時間は水温の影響を受
けるので２５℃に換算する。ＭＦ値は、菌体を含む水中
の微量懸濁物質濃度の指標であり、この値が小さいほど
菌体を含む水中の微量懸濁物質の濃度は低いことを意味
している。The processing results are shown in Table 1. The MF value is the time (seconds) required for suction filtration of 1.0 L of sample water with a membrane filter having a pore diameter of 0.45 μm and a diameter of 47 mm at a pressure of −67 kPa. Since the filtration time is affected by the water temperature, it is converted to 25 ° C. The MF value is an index of the concentration of a trace suspended substance in water containing cells, and the smaller this value is, the lower the concentration of the trace suspended substance in water containing cells is.
【００２０】比較例 実施例と同じ半導体洗浄排水の生物処理水を、精密濾過
膜モジュールによって処理した。処理に用いた精密濾過
膜モジュールの仕様と処理条件を下記に示す。 精密濾過膜モジュール 三菱レイヨン(株)製 ステラポアーＧ UMF-824WI（商品
名） 材質及び形状 ポリエチレン多孔質中空糸膜 孔径 0.1μｍ 寸法 110 mmφ×830 mmH, 有効膜面積 8 m2 通水流量 60 L/h 逆洗頻度 １回/60 分, 逆洗時間 3 分 処理結果を第１表に示す。Comparative Example The same biologically treated water as the semiconductor washing wastewater as in the example was treated by the microfiltration membrane module. The specifications and processing conditions of the microfiltration membrane module used for processing are shown below. Microfiltration membrane module Mitsubishi Rayon Co., Ltd. Stellapore G UMF-824WI (trade name) Material and shape Polyethylene porous hollow fiber membrane Pore diameter 0.1 μm Dimensions 110 mmφ × 830 mmH, effective membrane area 8 m 2 Water flow rate 60 L / h Backwash frequency 1 time / 60 minutes, backwash time 3 minutes Table 1 shows the treatment results.
【００２１】[0021]
【表１】 [Table 1]
【００２２】上記実施例及び比較例から明らかなよう
に、本発明方法によれば半導体洗浄排水中の有機物、有
機物の分解過程で増殖した菌体を効果的に除去すること
ができる。As is clear from the above Examples and Comparative Examples, according to the method of the present invention, it is possible to effectively remove the organic substances in the semiconductor cleaning wastewater and the bacterial cells grown in the process of decomposing the organic substances.
【００２３】[0023]
【発明の効果】本発明の半導体洗浄排水中の有機物除去
方法によれば、半導体洗浄排水中の有機物を生物処理し
た際に処理水中に残留する剥離した菌体を、繁殖させる
ことなく効率よく除去できる。EFFECTS OF THE INVENTION According to the method for removing organic matter in semiconductor cleaning wastewater of the present invention, the detached bacterial cells remaining in the treated water when the organic matter in the semiconductor cleaning wastewater is biologically treated are efficiently removed without breeding. it can.
【図１】図１は本発明の半導体洗浄排水の回収方法の概
略系統図の一例である。FIG. 1 is an example of a schematic system diagram of a semiconductor cleaning wastewater recovery method of the present invention.
【図２】図２は実施例に用いた生物処理装置の系統図で
ある。FIG. 2 is a systematic diagram of a biological treatment apparatus used in Examples.
───────────────────────────────────────────────────── 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 1/28 Ｆ 1/42 Ｄ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication C02F 1/28 F 1/42 D
Claims (3)
水製造工程に供給するための半導体洗浄排水の回収方法
において、該半導体洗浄排水を生物反応槽で生物処理し
て生成する処理水を、ＯＨ形陰イオン交換樹脂と接触処
理させることを特徴とする半導体洗浄排水の回収方法。1. A method of recovering semiconductor cleaning wastewater for biological treatment of the semiconductor cleaning wastewater and then supplying it to the ultrapure water production process, wherein treated water produced by biologically treating the semiconductor cleaning wastewater in a biological reaction tank is used. A method for recovering wastewater from semiconductor cleaning, which comprises contacting with an OH type anion exchange resin.
性陰イオン交換樹脂であることを特徴とする請求項１記
載の半導体洗浄排水の回収方法。2. The method for recovering semiconductor cleaning wastewater according to claim 1, wherein the OH type anion exchange resin is an OH type strongly basic anion exchange resin.
陰イオン交換樹脂が架橋度２〜１０％のゲル型のＯＨ形
強塩基性陰イオン交換樹脂であることを特徴とする請求
項１記載の半導体洗浄排水の回収方法。3. The OH type anion exchange resin used as the OH type anion exchange resin is a gel type OH type strongly basic anion exchange resin having a crosslinking degree of 2 to 10%. Recovery method of semiconductor cleaning wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02450795A JP3746803B2 (en) | 1995-01-20 | 1995-01-20 | Semiconductor cleaning wastewater collection method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02450795A JP3746803B2 (en) | 1995-01-20 | 1995-01-20 | Semiconductor cleaning wastewater collection method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08197094A true JPH08197094A (en) | 1996-08-06 |
| JP3746803B2 JP3746803B2 (en) | 2006-02-15 |
Family
ID=12140102
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02450795A Expired - Fee Related JP3746803B2 (en) | 1995-01-20 | 1995-01-20 | Semiconductor cleaning wastewater collection method |
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| Country | Link |
|---|---|
| JP (1) | JP3746803B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002336886A (en) * | 2001-05-11 | 2002-11-26 | Kurita Water Ind Ltd | Ultrapure water production equipment and ultrapure water production method |
| JP2008229484A (en) * | 2007-03-20 | 2008-10-02 | Kurita Water Ind Ltd | A method for treating concentrated wastewater from a pure water production apparatus and a treatment apparatus for the concentrated wastewater. |
| DE102008009219A1 (en) | 2008-02-06 | 2009-08-13 | Christ Water Technology Ag | Treatment of water with microorganisms |
| CN103145268A (en) * | 2013-03-25 | 2013-06-12 | 上海华强环保设备工程有限公司 | Plant water conservation and usage system in semiconductor industry |
| JP2016117523A (en) * | 2014-12-22 | 2016-06-30 | オルガノ株式会社 | Ion exchange resin filling method, ion exchange resin filling device, and ion exchange resin storage method |
-
1995
- 1995-01-20 JP JP02450795A patent/JP3746803B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002336886A (en) * | 2001-05-11 | 2002-11-26 | Kurita Water Ind Ltd | Ultrapure water production equipment and ultrapure water production method |
| JP2008229484A (en) * | 2007-03-20 | 2008-10-02 | Kurita Water Ind Ltd | A method for treating concentrated wastewater from a pure water production apparatus and a treatment apparatus for the concentrated wastewater. |
| DE102008009219A1 (en) | 2008-02-06 | 2009-08-13 | Christ Water Technology Ag | Treatment of water with microorganisms |
| EP2247540A2 (en) * | 2008-02-06 | 2010-11-10 | Christ Water Technology Ag | Processing of water using microorganisms |
| CN103145268A (en) * | 2013-03-25 | 2013-06-12 | 上海华强环保设备工程有限公司 | Plant water conservation and usage system in semiconductor industry |
| JP2016117523A (en) * | 2014-12-22 | 2016-06-30 | オルガノ株式会社 | Ion exchange resin filling method, ion exchange resin filling device, and ion exchange resin storage method |
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| Publication number | Publication date |
|---|---|
| JP3746803B2 (en) | 2006-02-15 |
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