JP2002336887A - Extrapure water making device and extrapure water making method - Google Patents
Extrapure water making device and extrapure water making methodInfo
- Publication number
- JP2002336887A JP2002336887A JP2001141892A JP2001141892A JP2002336887A JP 2002336887 A JP2002336887 A JP 2002336887A JP 2001141892 A JP2001141892 A JP 2001141892A JP 2001141892 A JP2001141892 A JP 2001141892A JP 2002336887 A JP2002336887 A JP 2002336887A
- Authority
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- Japan
- Prior art keywords
- water
- activated carbon
- carbon tower
- biological activated
- tower
- 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.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Biological Treatment Of Waste Water (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は超純水製造装置及び
超純水製造方法に係り、特に、有機物（ＴＯＣ）濃度が
きわめて低い超純水を製造することができる超純水製造
装置及び超純水製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultrapure water production apparatus and an ultrapure water production method, and more particularly to an ultrapure water production apparatus and an ultrapure water production apparatus capable of producing ultrapure water having an extremely low organic matter (TOC) concentration. It relates to a method for producing pure water.
【０００２】[0002]
【従来の技術】従来、半導体洗浄用水として用いられて
いる超純水は、図２に示すように前処理システム１、一
次純水系システム２、サブシステム３から構成される超
純水製造装置で原水（工業用水、市水、井水等）を処理
することにより製造される。図２において各システムの
役割は次の通りである。2. Description of the Related Art Conventionally, ultrapure water used as semiconductor cleaning water is an ultrapure water producing apparatus comprising a pretreatment system 1, a primary pure water system 2, and a subsystem 3, as shown in FIG. It is manufactured by treating raw water (industrial water, city water, well water, etc.). In FIG. 2, the role of each system is as follows.
【０００３】凝集、加圧浮上（沈殿）、濾過（膜濾過）
装置などよりなる前処理システム１では、原水中の懸濁
物質やコロイド物質の除去を行う。また、この過程では
高分子系有機物、疎水性有機物などの除去も可能であ
る。Coagulation, pressure flotation (sedimentation), filtration (membrane filtration)
In the pretreatment system 1 including devices and the like, suspended substances and colloid substances in raw water are removed. In this process, it is also possible to remove high molecular organic substances, hydrophobic organic substances, and the like.
【０００４】逆浸透膜分離装置、脱気装置及びイオン交
換装置（混床式又は４床５塔式など）を備える一次純水
系システム２では、原水中のイオンや有機成分の除去を
行う。なお、逆浸透膜分離装置では、塩類を除去すると
共に、イオン性、コロイド性のＴＯＣを除去する。イオ
ン交換装置では、塩類を除去すると共にイオン交換樹脂
によって吸着又はイオン交換されるＴＯＣ成分の除去を
行う。脱気装置では無機系炭素（ＩＣ）、溶存酸素の除
去を行う。[0004] In a primary pure water system 2 provided with a reverse osmosis membrane separation device, a degassing device, and an ion exchange device (such as a mixed-bed type or a four-bed five-column type), ions and organic components in raw water are removed. The reverse osmosis membrane separator removes salts and ionic and colloidal TOC. The ion exchange device removes salts and removes TOC components adsorbed or ion-exchanged by the ion exchange resin. The deaerator removes inorganic carbon (IC) and dissolved oxygen.
【０００５】低圧紫外線酸化装置、イオン交換純水装置
及び限外濾過膜分離装置を備えるサブシステム３では、
水の純度をより一層高め超純水にする。なお、低圧紫外
線酸化装置では、低圧紫外線ランプより出される１８５
ｎｍの紫外線によりＴＯＣを有機酸、さらにはＣＯ２ま
で分解する。分解により生成した有機物及びＣＯ２は後
段のイオン交換樹脂で除去される。限外濾過膜分離装置
では、微粒子が除去され、イオン交換樹脂の流出粒子も
除去される。[0005] In a subsystem 3 including a low-pressure ultraviolet oxidation apparatus, an ion-exchange pure water apparatus, and an ultrafiltration membrane separation apparatus,
Further increase the purity of water to ultrapure water. In the low-pressure ultraviolet oxidation device, 185 emitted from the low-pressure ultraviolet lamp is used.
The TOC is decomposed into organic acids and further to CO 2 by ultraviolet light of nm. Organic matter and CO 2 generated by the decomposition are removed by a subsequent ion exchange resin. In the ultrafiltration membrane separation device, the fine particles are removed, and the outflow particles of the ion exchange resin are also removed.
【０００６】このような従来の超純水製造装置で得られ
る超純水のＴＯＣ濃度は、おおむね１μｇ／Ｌ程度であ
る。[0006] The TOC concentration of ultrapure water obtained by such a conventional ultrapure water production apparatus is about 1 µg / L.
【０００７】ところで、ＬＳＩの超微細化、高集積化に
伴い、超ＬＳＩチップ製造における洗浄水としての超純
水中の不純物の影響はより大きくなってきている。超Ｌ
ＳＩチップ不良の大部分はパターン欠陥であり、その主
な原因は超純水中の不純物である。超純水中の不純物は
主に低分子系有機物であり、従って、低分子系有機物成
分をより一層効率良く除去する高性能の超純水製造装置
が必要となってくる。[0007] With the miniaturization and high integration of LSIs, the influence of impurities in ultrapure water as cleaning water in the manufacture of VLSI chips has become greater. Super L
The majority of SI chip failures are pattern defects, and the main cause is impurities in ultrapure water. The impurities in the ultrapure water are mainly low molecular organic substances, and therefore, a high-performance ultrapure water production apparatus that removes the low molecular organic components more efficiently is required.
【０００８】特開平６−１２６２７１号公報には、一次
純水系システムに、通常の活性炭と細孔径２０〜１００
０Åの細孔を全細孔の５〜１０％以上持つ高性能活性炭
とシリカアルミナ系吸着剤との３層からなる多層吸着装
置を設置することにより、逆浸透膜分離装置やイオン交
換装置では除去することが難しい有機物を効率良く除去
することが報告されているが、この方法は単なる吸着法
であるため、充填剤の吸着能が飽和に達してしまうと破
過してしまうという欠点がある。また、吸着によるＴＯ
Ｃ除去効果が期待できるのは、初期吸着と呼ばれる通水
開始から約２ヶ月ぐらいの間であり、それ以降の除去効
果は期待できないという欠点もある。[0008] Japanese Patent Application Laid-Open No. 6-126271 discloses that a primary pure water system is provided with ordinary activated carbon and a pore size of 20 to 100.
By installing a multi-layer adsorption apparatus consisting of three layers of high-performance activated carbon having 5% or more of 0% of the total pores and silica-alumina-based adsorbent, it can be removed by a reverse osmosis membrane separation apparatus or an ion exchange apparatus. Although it has been reported that organic substances which are difficult to remove are efficiently removed, this method is a mere adsorption method, and has a drawback that when the adsorption capacity of the filler reaches saturation, it breaks through. In addition, TO by adsorption
The effect of removing C can be expected only for about two months from the start of water flow, which is called initial adsorption, and there is a drawback that the effect of removing C after that cannot be expected.
【０００９】[0009]
【発明が解決しようとする課題】本発明は上記従来の問
題点を解決し、原水中の有機物、特に低分子系有機物成
分を効率的に除去することができ、ＴＯＣ濃度がきわめ
て低く、高純度な超純水を製造することができる超純水
製造装置及び超純水製造方法を提供することを目的とす
る。SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems and can efficiently remove organic substances, particularly low molecular weight organic substances, in raw water, have a very low TOC concentration, and have a high purity. It is an object of the present invention to provide an ultrapure water production apparatus and an ultrapure water production method capable of producing ultrapure water.
【００１０】[0010]
【課題を解決するための手段】本発明の超純水製造装置
は、一次純水系システムと、該一次純水系システムの処
理水を処理するサブシステムとを有する超純水製造装置
において、該一次純水系システムに生物活性炭塔が設け
られている超純水製造装置であって、該生物活性炭塔
は、制限された量の抗菌剤の存在下に原水を処理して、
原水中の有機物を生物的に分解するものであることを特
徴とする。An ultrapure water producing apparatus according to the present invention is an ultrapure water producing apparatus having a primary pure water system and a subsystem for treating treated water of the primary pure water system. An ultrapure water production apparatus provided with a biological activated carbon tower in a pure water system, wherein the biological activated carbon tower processes raw water in the presence of a limited amount of an antibacterial agent,
It is characterized by biologically decomposing organic matter in raw water.
【００１１】本発明の超純水製造方法は、原水を一次純
水系システムで処理した後サブシステムで処理する超純
水製造方法において、該一次純水系システムにおいて、
原水を制限された量の抗菌剤の存在下に生物活性炭塔に
通水して原水中の有機物を生物的に分解することを特徴
とする。An ultrapure water production method according to the present invention is an ultrapure water production method in which raw water is treated in a primary pure water system and then processed in a subsystem.
It is characterized in that raw water is passed through a biological activated carbon tower in the presence of a limited amount of an antibacterial agent to biologically decompose organic matter in the raw water.
【００１２】本発明は、超純水中に含まれる有機物が低
分子系有機物であることに注目し、低分子有機物の分解
性能に優れている生物処理と活性炭による吸着処理効果
を併せ持った生物活性炭塔を一次純水系システムに導入
することにより、超純水中のＴＯＣ濃度の低減を可能と
した。The present invention focuses on the fact that the organic matter contained in ultrapure water is a low molecular weight organic substance. By introducing the tower into the primary pure water system, it was possible to reduce the TOC concentration in ultrapure water.
【００１３】この生物活性炭塔の有機物除去機構は 活性炭による有機物吸着効果 生物膜による有機物分解効果 活性炭内の微生物が活性炭に吸着した有機物を分解
して細孔容積を回復させる生物再生効果 の３つの機構よりなり、生物活性炭を使用することによ
って、活性炭自体の吸着能が飽和に達するまでの時間は
大幅に延長される。[0013] The organic matter removal mechanism of this biological activated carbon tower has three mechanisms: an organic matter adsorption effect by activated carbon; an organic matter decomposing effect by biofilm; and a biological regeneration effect in which microorganisms in activated carbon decompose organic matter adsorbed on activated carbon to recover pore volume. By using biological activated carbon, the time required for the activated carbon itself to reach its adsorption capacity is greatly extended.
【００１４】このような生物活性炭塔では、塔内での微
生物の繁殖により、塔内の圧力損失の増加が懸念される
が、本発明では、抗菌剤の存在下に処理を行うため、塔
内での微生物の必要以上の繁殖は抑制され、このような
目詰まりは抑制される。また、酸化剤等の抗菌剤が生物
活性炭塔内で分解される際に酸素が放出されるため、塔
内が溶存酸素不足となることもない。In such a biological activated carbon tower, there is a concern that the pressure loss in the tower may increase due to the propagation of microorganisms in the tower. However, in the present invention, the treatment is carried out in the presence of an antibacterial agent. Unnecessary reproduction of microorganisms in the soil is suppressed, and such clogging is suppressed. Further, since oxygen is released when an antibacterial agent such as an oxidizing agent is decomposed in the biological activated carbon tower, the inside of the tower does not become short of dissolved oxygen.
【００１５】また、生物活性炭塔の後段に設置される逆
浸透膜分離装置及びイオン交換装置においては、生物活
性炭塔からリークする余剰菌による目詰まりが懸念され
るが、上述の如く、本発明では抗菌剤によりある一定以
上の菌が生物活性炭塔内に増殖することを抑制している
ため、菌体のリークは最小限に抑えられ、逆浸透膜分離
装置やイオン交換装置が目詰まりを起こすことはない。Further, in the reverse osmosis membrane separation device and the ion exchange device installed at the subsequent stage of the biological activated carbon tower, clogging due to excess bacteria leaking from the biological activated carbon tower is a concern. Antimicrobial agents prevent more than a certain amount of bacteria from growing in the biological activated carbon tower, minimizing cell leakage and clogging reverse osmosis membrane separation devices and ion exchange devices. There is no.
【００１６】生物活性炭塔において生分解性有機物はほ
ぼ完全に分解除去されるため、その後段での微生物の繁
殖を抑制することも可能となる。Since the biodegradable organic matter is almost completely decomposed and removed in the biological activated carbon tower, it is possible to suppress the growth of microorganisms in the subsequent stage.
【００１７】なお、本発明において、抗菌剤の存在量を
制限することはきわめて重要であり、抗菌剤の存在量が
多過ぎると生物活性炭塔内の菌を死滅させてしまい、生
物活性炭塔としての機能を得ることができなくなる。本
発明においては、このような制限された量の抗菌剤によ
り、生物活性炭塔内の菌の一部は死滅又は活性を失う
が、残部の菌は若干活性が低下するもののなお活性を有
するような状態に維持する。In the present invention, it is extremely important to limit the amount of the antibacterial agent. If the amount of the antibacterial agent is too large, the bacteria in the activated carbon tower will be killed, and the activity of the activated carbon tower will be reduced. The function cannot be obtained. In the present invention, such a limited amount of the antibacterial agent causes some of the bacteria in the biological activated carbon tower to die or lose their activity, while the remaining bacteria have a slightly reduced activity but still have activity. Keep in state.
【００１８】一般に、生物活性炭塔中の菌体付着量は処
理条件によっても異なるが、抗菌剤を存在させない場
合、１０６個／ｇ−活性炭以上となる。本発明では、制
限された量の抗菌剤の存在下で、生物活性炭塔中の菌体
付着量をこれよりも少なく、例えば１０４個／ｇ以上１
０６個／ｇ未満となるように、微生物の増殖を抑制する
ことが好ましい。[0018] Generally, cell adhesion amount in biological activated carbon column varies depending processing conditions, if the absence of an antimicrobial agent, a 106 / g- activated carbon or more. In the present invention, in the presence of a limited amount of an antibacterial agent, the amount of cells adhering to the biological activated carbon tower is smaller than this, for example, 10 4 cells / g or more and 1
0 to less than 6 / g, it is preferable to inhibit the growth of microorganisms.
【００１９】このような抗菌剤の存在量は、用いる抗菌
剤や、処理条件等によっても異なるが、例えば塩素系抗
菌剤を用いた場合、生物活性炭塔に流入する水の残留塩
素濃度が０．５〜５ｍｇ／Ｌ程度となるようにするのが
好ましい。The amount of such an antibacterial agent varies depending on the antibacterial agent to be used, the treatment conditions, and the like. For example, when a chlorine-based antibacterial agent is used, the residual chlorine concentration of water flowing into the biological activated carbon tower is 0.1%. It is preferable that the concentration be about 5 to 5 mg / L.
【００２０】[0020]
【発明の実施の形態】以下に図面を参照して本発明の超
純水製造装置及び超純水製造方法の実施の形態を詳細に
説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the ultrapure water production apparatus and the ultrapure water production method of the present invention will be described below in detail with reference to the drawings.
【００２１】図１は本発明の超純水製造装置の実施の形
態を示す系統図である。FIG. 1 is a system diagram showing an embodiment of the ultrapure water production apparatus of the present invention.
【００２２】一次純水系システム２の原水は、工水、市
水、井水、或いはこれに回収水（超純水のコースポイン
トで回収された使用済超純水）を混合した水を凝集、加
圧浮上（沈殿）、濾過装置等よりなる前処理システム１
で処理して得られた水である。The raw water of the primary pure water system 2 is made up of industrial water, city water, well water or water obtained by mixing recovered water (used ultrapure water collected at a course point of ultrapure water). Pretreatment system 1 consisting of pressure flotation (sedimentation), filtration device, etc.
Is water obtained by the treatment described above.
【００２３】生物活性炭塔に流入する水を前処理してお
くことにより、生物活性炭塔の活性炭の寿命が長くな
る。即ち、凝集沈殿処理等の前処理を行っていない水に
は、有機物中の生分解性の低い高分子系有機物成分の割
合が多く、このような水を生物活性炭塔に通水すると、
前述の生物による有機物の分解及び活性炭の再生効果が
得られないために、活性炭が早期に破過してしまう。こ
れに対し、本発明では、生物活性炭塔を一次純水系シス
テム２に設け、前処理を経た水を生物活性炭塔に通水す
ることにより、高分子系有機物は前処理で除去され、低
分子系有機物は生物活性炭で除去される。しかも、この
低分子系有機物が生物活性炭で生物的に分解されるた
め、生物活性炭の寿命が著しく長い。By pre-treating the water flowing into the biological activated carbon tower, the life of the activated carbon in the biological activated carbon tower is extended. In other words, water that has not been subjected to a pretreatment such as coagulation and sedimentation treatment has a high proportion of a low-biodegradable high-molecular organic substance component in the organic substance.When such water is passed through a biological activated carbon tower,
Activated carbon breaks down early because the above-mentioned organisms do not have the effect of decomposing organic matter and regenerating activated carbon. On the other hand, in the present invention, the biological activated carbon tower is provided in the primary pure water system 2, and the water subjected to the pretreatment is passed through the biological activated carbon tower, whereby the high-molecular organic matter is removed by the pretreatment, and the low-molecular organic substance is removed. Organic matter is removed with biological activated carbon. In addition, since the low-molecular organic matter is biologically decomposed by the biologically activated carbon, the life of the biologically activated carbon is extremely long.
【００２４】生物活性炭塔は、生物活性炭塔給水の溶存
酸素濃度を高めるために、図１に示す如く、脱炭酸塔の
後段に設けることが好ましく、また、生物活性炭塔から
放出される余剰菌体の除去という観点から逆浸透膜分離
装置の前段に設置するのが好ましい。即ち、脱炭酸塔で
は、炭酸の除去のために一般に空気を吹き込むため、空
気中の酸素が水中に溶け込み、生物活性炭塔に必要な溶
存酸素を確保することができる。一般に、工水、市水、
井水、更には回収水を前処理して得られる水のＴＯＣ
は、１ｍｇ／Ｌ程度であるので、この脱炭酸塔で溶解す
る程度の酸素量で生物活性炭塔に必要な酸素量を十分に
まかなうことができる。また、本発明では、抗菌剤を存
在させることで生物活性炭塔からの菌体の流出を抑制す
るが、菌体の流出を完全に防止できるものではないた
め、後段の逆浸透膜分離手段で除去するようにするのが
好ましい。その他、生物活性炭塔の後段に余剰菌の繁殖
防止のため紫外線殺菌塔を設置しても良く、また生物活
性炭塔の後段で殺菌剤を添加しても良い。The biological activated carbon tower is preferably provided at the subsequent stage of the decarbonation tower as shown in FIG. 1 in order to increase the dissolved oxygen concentration in the feed water of the biological activated carbon tower. It is preferable to install it in the preceding stage of the reverse osmosis membrane separation device from the viewpoint of removal of odor. That is, in the decarbonation tower, since air is generally blown to remove carbonic acid, oxygen in the air dissolves in water, and dissolved oxygen required for the biological activated carbon tower can be secured. Generally, industrial water, city water,
TOC of water obtained by pre-processing well water and recovered water
Is about 1 mg / L, so that the amount of oxygen enough to be dissolved in the decarbonation tower can sufficiently cover the amount of oxygen required for the biological activated carbon tower. In the present invention, the presence of an antibacterial agent suppresses the outflow of cells from the biological activated carbon tower. However, this does not completely prevent the outflow of cells, so that the cells are removed by a reverse osmosis membrane separation means at the subsequent stage. It is preferable to do so. In addition, an ultraviolet disinfection tower may be provided at the subsequent stage of the biological activated carbon tower to prevent the propagation of surplus bacteria, and a bactericide may be added at the latter stage of the biological activated carbon tower.
【００２５】なお、生物活性炭塔から流出した菌体によ
る逆浸透膜分離装置の目詰まりを防止するために、生物
活性炭塔と逆浸透膜分離装置との間には保安フィルター
を設けることが望ましい。In order to prevent clogging of the reverse osmosis membrane separation device by the cells flowing out of the biological activated carbon tower, it is desirable to provide a security filter between the biological activated carbon tower and the reverse osmosis membrane separation device.
【００２６】生物活性炭塔に充填する活性炭種としては
石炭系、椰子殻系等のいずれでも良く、破砕炭、造粒
炭、成形炭、クロス状、繊維状等、その形状、種類等に
特に制限はない。The type of activated carbon to be filled in the biological activated carbon tower may be any of coal type, coconut shell type, etc., and is particularly limited to its shape and type such as crushed coal, granulated coal, molded coal, cloth, fiber and the like. There is no.
【００２７】生物活性炭塔への活性炭の充填方式は、流
動床、膨張層、固定床などのいずれでもよいが、菌体の
リークが少ないところから、固定床が好ましい。生物活
性炭塔の通水方式は上向流通水であっても下向流通水で
あっても良い。The activated carbon may be filled into the biological activated carbon tower by any of a fluidized bed, an expanded bed, a fixed bed and the like, but a fixed bed is preferred because there is little leakage of cells. The water flow method of the biological activated carbon tower may be upward flowing water or downward flowing water.
【００２８】生物活性炭塔の生物担持量は、通水初期の
状態でメタノール除去速度１０μｇ／Ｌ／ｍｉｎ以上を
達成できるようなものであることが好ましい。このメタ
ノール除去速度は、例えば、生物活性炭塔にＴＯＣとし
てメタノールを含有する水をＳＶ２０ｈｒ−１で通水し
たときの入口ＴＯＣ濃度と出口ＴＯＣ濃度とから、ＴＯ
Ｃ除去量を求め、これを滞留時間（ＨＲＴ）で除して求
められる。It is preferable that the biologically active amount of the biological activated carbon tower is such that a methanol removal rate of 10 μg / L / min or more can be achieved in the initial state of water flow. The methanol removal rate is determined, for example, from the TOC concentration at the inlet and the TOC concentration at the outlet when water containing methanol as TOC is passed through the biological activated carbon tower at SV20 hr -1.
The amount of C removed is determined and divided by the residence time (HRT).
【００２９】本発明においては、このような生物活性炭
塔に、制限された量の抗菌剤の存在下に原水を通水す
る。In the present invention, raw water is passed through such a biological activated carbon tower in the presence of a limited amount of an antibacterial agent.
【００３０】ここで、抗菌剤としては、殺菌剤、酸化剤
等が用いられるが、好ましくは、酸化剤であり、具体的
には、次亜塩素酸塩のような塩素系酸化剤や、オゾン、
過酸化水素などを用いることができる。Here, as the antibacterial agent, a bactericide, an oxidizing agent and the like are used. Preferably, the oxidizing agent is used. Specifically, a chlorine-based oxidizing agent such as hypochlorite, ozone ,
Hydrogen peroxide or the like can be used.
【００３１】本発明では、生物活性炭塔の給水中にこの
ような抗菌剤を存在させることにより、生物活性炭塔内
の菌体の過剰な増殖を抑制し、生物活性炭塔からの菌体
の流出を抑制する。ＴＯＣ除去効果と菌体の流出抑制効
果を得ることができる生物活性炭塔内の菌体付着量は、
１０４個／ｇ−活性炭以上１０６個／ｇ−活性炭未満で
ある。In the present invention, by allowing such an antibacterial agent to be present in the water supplied to the biological activated carbon tower, excessive growth of the cells in the biological activated carbon tower is suppressed, and the outflow of the cells from the biological activated carbon tower is prevented. Suppress. The amount of adhered cells in the biological activated carbon tower, which can obtain the TOC removal effect and the effect of suppressing the outflow of cells,
It is 10 4 pieces / g-activated carbon or more and less than 10 6 pieces / g-activated carbon.
【００３２】このような菌体付着量を得るための抗菌剤
濃度は、用いる抗菌剤の種類や処理条件等に応じても異
なるが、例えば塩素系酸化剤を用いた場合、生物活性炭
塔の給水（入口）の残留塩素濃度で０．５〜５ｍｇ／Ｌ
程度である。この残留塩素濃度が０．５ｍｇ／Ｌ未満で
は、生物活性炭塔内での菌体の増殖を抑制し得ず、５ｍ
ｇ／Ｌを超えると生物活性炭塔内の菌体が死滅してしま
い生物分解能を得ることができなくなる上に活性炭の劣
化で寿命が短縮することとなる。生物活性炭塔給水のよ
り好ましい残留塩素濃度は１〜３ｍｇ／Ｌである。The concentration of the antibacterial agent for obtaining such an amount of adhered cells varies depending on the kind of the antibacterial agent to be used, the treatment conditions, and the like. (Inlet) residual chlorine concentration of 0.5 to 5 mg / L
It is about. If the residual chlorine concentration is less than 0.5 mg / L, the growth of cells in the biological activated carbon tower cannot be suppressed, and
If the amount exceeds g / L, the cells in the biologically activated carbon tower will be killed, biodegradability cannot be obtained, and the life of the activated carbon will be shortened due to deterioration of the activated carbon. The more preferable residual chlorine concentration of the biological activated carbon tower feed water is 1 to 3 mg / L.
【００３３】従って、本発明では、生物活性炭塔の給水
の残留塩素濃度等の抗菌剤濃度がこのような濃度となる
ように適宜原水に抗菌剤を添加するが、一般に市水系原
水を用いる場合、市水には残留塩素が０．５ｍｇ／Ｌ程
度含まれているため、抗菌剤の添加が不要な場合もあ
る。しかし、市水以外の井水や工水、回収水を原水とす
る場合、或いは市水を用いる場合でもこれら市水や回収
水、工水等の割合が多く、原水の抗菌剤濃度が不足する
場合には、抗菌剤を添加する。Therefore, in the present invention, the antibacterial agent is appropriately added to the raw water so that the concentration of the antibacterial agent such as the residual chlorine concentration in the feed water of the biological activated carbon tower becomes such a concentration. Since city water contains about 0.5 mg / L of residual chlorine, it may not be necessary to add an antibacterial agent. However, when using well water, industrial water, and recovered water other than city water as raw water, or when using city water, the ratio of these city water, recovered water, industrial water, etc. is large, and the antibacterial agent concentration of raw water is insufficient. In some cases, an antimicrobial agent is added.
【００３４】抗菌剤の添加箇所は、生物活性炭塔の前段
であれば良く、特に制限はないが、抗菌剤の添加によ
り、生物活性炭塔に到るまでの配管やタンク内の微生物
の繁殖をも抑制する意味合いから、前処理システム１の
凝集槽の前段に添加することが好ましい。凝集槽の前段
で酸化剤を添加した場合には、原水由来のＦｅ，Ｍｎ等
を酸化剤により酸化させてその溶解度を低下させ、これ
により凝集沈殿によるＦｅ，Ｍｎの除去効率を高めるこ
ともできる。The location where the antibacterial agent is added is not particularly limited as long as it is in front of the biological activated carbon tower, and the addition of the antibacterial agent can also increase the growth of microorganisms in pipes and tanks up to the biological activated carbon tower. From the standpoint of suppression, it is preferable to add the compound to a stage preceding the coagulation tank of the pretreatment system 1. When an oxidizing agent is added in the previous stage of the coagulation tank, Fe, Mn, etc. derived from raw water are oxidized by the oxidizing agent to lower the solubility thereof, thereby improving the efficiency of removing Fe and Mn by coagulation sedimentation. .
【００３５】Ｆｅ，Ｍｎなどが除去されずに逆浸透膜分
離装置に通水されると、逆浸透膜がこれらの物質によっ
てファウリングを起こす可能性があるため、このように
予めＦｅ，Ｍｎを除去することは安定運転のために有利
である。If water is passed through the reverse osmosis membrane separator without removing Fe, Mn, etc., the reverse osmosis membrane may cause fouling due to these substances. Elimination is advantageous for stable operation.
【００３６】また、凝集沈殿のような前処理を必要とし
ない原水の場合には、原水タンクの入口側に抗菌剤を添
加するのが好ましい。In the case of raw water that does not require pretreatment such as coagulation and sedimentation, it is preferable to add an antibacterial agent to the inlet side of the raw water tank.
【００３７】生物活性炭塔への通水速度は、ＳＶ５〜３
０ｈｒ−１程度とするのが好ましい。この生物活性炭塔
の給水の水温は１０〜３５℃、ｐＨは４〜８であること
が好ましく、従って、必要に応じて、生物活性炭塔の前
段に熱交換器やｐＨ調整剤添加手段を設けることが望ま
しい。The water flow rate to the biological activated carbon tower is SV 5 to 3
It is preferably set to about 0 hr -1 . The water temperature of the feed water of the biological activated carbon tower is preferably 10 to 35 ° C., and the pH is preferably 4 to 8. Therefore, if necessary, a heat exchanger or a pH adjuster adding means may be provided in the preceding stage of the biological activated carbon tower. Is desirable.
【００３８】なお、図示の通り、生物活性炭塔を一次純
水系システムの脱炭酸塔と逆浸透膜分離装置との間に設
けることにより、脱炭酸塔による溶存酸素供給及び逆浸
透膜分離装置による流出菌体の捕捉を行うことができ
る。As shown in the figure, by providing a biological activated carbon tower between the decarbonation tower of the primary pure water system and the reverse osmosis membrane separator, the supply of dissolved oxygen by the decarbonation tower and the outflow by the reverse osmosis membrane separator are performed. Bacteria can be captured.
【００３９】[0039]
【実施例】以下に実験例、実施例及び比較例を挙げて、
本発明をより具体的に説明する。EXAMPLES Hereinafter, experimental examples, examples and comparative examples will be described.
The present invention will be described more specifically.
【００４０】実験例１ 市水（ＴＯＣ濃度１ｍｇ／Ｌ、塩素濃度０．６ｍｇ／
Ｌ、ｐＨ６．８、水温２０℃）を原水として、通常の活
性炭塔と生物活性炭塔とにそれぞれ通水ＳＶ：２０ｈｒ
−１，通水速度２０Ｌ／ｈｒで１年間通水し、ＴＯＣの
除去性能を比較する実験を行い、結果を図３に示した。Experimental Example 1 City water (TOC concentration 1 mg / L, chlorine concentration 0.6 mg / L
L, pH 6.8, water temperature 20 ° C.) as raw water and passed through a normal activated carbon tower and a biological activated carbon tower, respectively SV: 20 hr
−1 , water was passed at a flow rate of 20 L / hr for one year, and an experiment was performed to compare the TOC removal performance. The results are shown in FIG. 3.
【００４１】なお、活性炭塔及び生物活性炭塔に用いた
活性炭種はクラレケミカル社製石炭系活性炭「ＫＷ１０
−３２」であり、活性炭充填量は１Ｌとした。生物活性
炭塔は、メタノール分解除去速度１０μｇ／Ｌ／ｍｉｎ
となるように生物を担持させたものである。原水には、
活性炭塔又は生物活性炭塔の入口の残留塩素濃度が１ｍ
ｇ／Ｌとなるように、ＮａＣｌＯを添加した。また、Ｔ
ＯＣ除去性能は、活性炭塔又は生物活性炭塔の入口のＴ
ＯＣ濃度と出口のＴＯＣ濃度とをアナテル社製「Ａ−１
０００ＸＰ」で測定し、（出口ＴＯＣ濃度÷入口ＴＯＣ
濃度）でＴＯＣのリーク率を求めることにより調べた。The activated carbon used in the activated carbon tower and the biological activated carbon tower was a coal-based activated carbon “KW10” manufactured by Kuraray Chemical Co., Ltd.
-32 ", and the activated carbon filling amount was 1 L. The biological activated carbon tower has a methanol decomposition removal rate of 10 μg / L / min.
An organism is supported so that In the raw water,
Residual chlorine concentration at the entrance of activated carbon tower or biological activated carbon tower is 1m
NaClO was added to give g / L. Also, T
The OC removal performance is determined by the T at the entrance of the activated carbon tower or the biological activated carbon tower.
The OC concentration and the TOC concentration at the outlet were determined by "A-1"
000XP ”, and the value of (TOC concentration at outlet ÷ TOC at inlet)
Concentration) to determine the TOC leak rate.
【００４２】図３より明らかなように、通水開始後１ヶ
月ぐらいまでは両者の結果に大きな相違は見られなかっ
たが、１ヶ月を過ぎたあたりから両者の除去性能には開
きが生じ、通常の活性炭塔では通水開始２００日で原水
ＴＯＣに対し９０％以上がリークした。しかし、生物活
性炭塔では６５％と通常の活性炭塔に比べ１．４倍のＴ
ＯＣ除去性能を発揮した。As is apparent from FIG. 3, no significant difference was observed between the two results about one month after the start of water flow, but after about one month, there was a difference in the removal performance of the two. In a normal activated carbon tower, 90% or more of the raw water TOC leaked 200 days after the start of water flow. However, the biological activated carbon tower has a T value of 65%, which is 1.4 times that of a normal activated carbon tower.
It exhibited OC removal performance.
【００４３】これは、通常の活性炭塔では、活性炭によ
る吸着性能のみでＴＯＣを除去するため、早期に活性炭
の吸着能が飽和し、ＴＯＣがリークしてくるのに対し
て、生物活性炭塔では、活性炭による吸着のみならず、
生物によるＴＯＣ分解と生物による活性炭の吸着能の再
生作用が得られ、長期に亘りＴＯＣ除去能が維持される
ことによるものである。This is because, in a normal activated carbon tower, TOC is removed only by the adsorption performance by activated carbon, so that the activated carbon adsorption capacity is saturated and TOC leaks at an early stage, whereas in a biological activated carbon tower, Not only adsorption by activated carbon,
This is because the TOC decomposition by the organism and the regeneration of the ability to adsorb activated carbon by the organism are obtained, and the TOC removal ability is maintained for a long time.
【００４４】実験例２ 市水を原水として、実験例１で用いたものと同様の生物
活性炭塔に同様の条件で通水した。このとき生物活性炭
塔を１日１回の頻度で逆洗し、１日当たりの圧力損失の
増加の程度を調べ、結果を図４に示した（なお、図４に
おいて、０．１ｋｇｆ／ｃｍ２／日は約１０４Ｐａ／日
である。）。Experimental Example 2 Using city water as raw water, water was passed through the same biological activated carbon tower as used in Experimental Example 1 under the same conditions. At this time, the biological activated carbon tower was backwashed once a day, and the degree of increase in pressure loss per day was examined. The results are shown in FIG. 4 (in FIG. 4, 0.1 kgf / cm 2 / The day is about 10 4 Pa / day).
【００４５】比較のため、市水にＮａＨＳＯ３を添加し
て残留塩素濃度を０ｍｇ／Ｌとしたこと以外は上記と同
様にして通水実験を行い、１日当たりの圧力損失の増加
の程度を調べ、結果を図４に示した。For comparison, a water flow experiment was carried out in the same manner as above except that NaHSO 3 was added to city water to reduce the residual chlorine concentration to 0 mg / L, and the degree of increase in the pressure loss per day was examined. The results are shown in FIG.
【００４６】図４より、生物活性炭塔入口の残留塩素濃
度が０ｍｇ／Ｌでは、生物活性炭塔内での菌体の増殖が
激しく、生物活性炭塔の目詰まりで圧力損失が増大する
が、残留塩素濃度を１ｍｇ／Ｌとすることで、菌体の過
度な増殖を抑制して、生物活性炭塔内の圧力損失の増加
を抑制することができることがわかる。As shown in FIG. 4, when the residual chlorine concentration at the entrance of the biological activated carbon tower is 0 mg / L, the bacterial growth in the biological activated carbon tower is intense, and the pressure loss increases due to clogging of the biological activated carbon tower. It can be seen that by setting the concentration to 1 mg / L, excessive growth of the cells can be suppressed, and an increase in pressure loss in the biological activated carbon tower can be suppressed.
【００４７】なお、通水期間中の生物活性炭塔内の活性
炭に対する菌体付着量を蛍光色素を用いた直接計数法に
より調べたところ、残留塩素濃度を１ｍｇ／Ｌとした場
合には、１０５〜１０６個／ｇの範囲に維持されていた
が、残留塩素濃度を０ｍｇ／Ｌとした場合には、１０７
〜１０８個／ｇに増殖していた。The amount of bacterial cells attached to activated carbon in the biological activated carbon tower during the water flow period was examined by a direct counting method using a fluorescent dye. As a result, when the residual chlorine concentration was 1 mg / L, 10 5 10 6 / g had been maintained in the range of, in the case where the residual chlorine concentration of 0 mg / L, the 10 7
10 had grown to eight / g.
【００４８】実施例１ 市水（ＴＯＣ濃度１ｍｇ／Ｌ、ｐＨ６．８、水温２０
℃、塩素濃度０．６ｍｇ／Ｌ）を、２ｍ３／ｈｒの処理
量で一次純水系システムとしての脱炭酸塔、生物活性炭
塔、逆浸透膜分離装置、混床式イオン交換装置、脱気装
置及び逆浸透膜分離装置に順次通水した後、サブシステ
ムとしての低圧紫外線酸化装置、イオン交換純水装置、
及び限外濾過膜分離装置に順次通水して処理して超純水
を製造する超純水製造装置において、生物活性炭塔の出
口水のＴＯＣ濃度と、得られた超純水（限外濾過膜分離
装置の出口水）のＴＯＣ濃度を調べ、結果を表１に示し
た。ＴＯＣ濃度はアナテル社製「Ａ−１０００ＸＰ」を
用いて測定した。Example 1 City water (TOC concentration 1 mg / L, pH 6.8, water temperature 20)
C., chlorine concentration 0.6 mg / L) at a treatment rate of 2 m 3 / hr, a decarbonation tower, a biological activated carbon tower, a reverse osmosis membrane separation apparatus, a mixed bed type ion exchange apparatus, and a deaeration apparatus as a primary pure water system. And after passing water sequentially through the reverse osmosis membrane separation device, low pressure ultraviolet oxidation device as a subsystem, ion exchange pure water device,
And an ultrapure water production apparatus for producing ultrapure water by sequentially passing water through an ultrafiltration membrane separation apparatus and treating the TOC concentration of the outlet water of the biological activated carbon tower with the obtained ultrapure water (ultrafiltration). The TOC concentration of the outlet water of the membrane separation device was examined, and the results are shown in Table 1. The TOC concentration was measured using "A-1000XP" manufactured by Anatel.
【００４９】なお、用いた生物活性炭塔は、実験例１で
用いたものと同様の活性炭種及びメタノール除去性能の
ものであり、通水ＳＶは２０ｈｒ−１とした。また、市
水にはＮａＣｌＯを添加して生物活性炭塔の入口の残留
塩素濃度が１ｍｇ／Ｌとなるように調整した。The biological activated carbon tower used had the same activated carbon type and methanol removal performance as those used in Experimental Example 1, and the water flow SV was 20 hr -1 . In addition, NaClO was added to the city water so that the residual chlorine concentration at the entrance of the biological activated carbon tower was adjusted to 1 mg / L.
【００５０】比較例１ 実施例１において、生物活性炭塔の代りに通常の活性炭
塔を用いたこと以外は同様にして超純水の製造を行い、
活性炭塔の出口水のＴＯＣ濃度と得られた超純水のＴＯ
Ｃ濃度を調べ、結果を表１に示した。Comparative Example 1 Ultrapure water was produced in the same manner as in Example 1 except that a normal activated carbon tower was used instead of the biological activated carbon tower.
TOC concentration of outlet water of activated carbon tower and TO of obtained ultrapure water
The C concentration was examined, and the results are shown in Table 1.
【００５１】比較例２ 実施例１において、ＮａＨＳＯ３を添加することにより
生物活性炭塔の入口の残留塩素濃度を０ｍｇ／Ｌとした
こと以外は同様にして超純水の製造を行い、活性炭塔の
出口水のＴＯＣ濃度と得られた超純水のＴＯＣ濃度を調
べ、結果を表１に示した。Comparative Example 2 Ultrapure water was produced in the same manner as in Example 1 except that the residual chlorine concentration at the inlet of the biological activated carbon tower was changed to 0 mg / L by adding NaHSO 3 . The TOC concentration of the outlet water and the TOC concentration of the obtained ultrapure water were examined, and the results are shown in Table 1.
【００５２】[0052]
【表１】 [Table 1]
【００５３】表１より次のことが明らかである。The following is clear from Table 1.
【００５４】即ち、活性炭塔で処理した比較例１では、
通水日数に伴いＴＯＣ値が増加し超純水中のＴＯＣ値は
１μｇ／Ｌ程度で安定した。これは図３で示した活性炭
塔での傾向と同じである。一方、生物活性炭塔を用いた
実施例１においては通水日数によらず超純水のＴＯＣ濃
度は０．３μｇ／Ｌ程度で安定しており、図３で示し
た、生物活性炭塔単独の時とは傾向が異なる。これは、
一部のＴＯＣ成分が生物活性炭塔内で完全に分解、吸着
除去されなかったとしても、生物活性炭塔を通過するこ
とにより生物によって何らかの形態変化を受け、後段の
逆浸透膜分離装置やイオン交換装置で除去可能物質に変
化したため、ＴＯＣ濃度が低い値で安定するためと考え
られる。That is, in Comparative Example 1, which was treated with an activated carbon tower,
The TOC value increased with the passage of water, and the TOC value in the ultrapure water was stabilized at about 1 μg / L. This is the same as the tendency in the activated carbon tower shown in FIG. On the other hand, in Example 1 using the biological activated carbon tower, the TOC concentration of the ultrapure water was stable at about 0.3 μg / L regardless of the number of days of water passage. And the tendency is different. this is,
Even if some TOC components are not completely decomposed and adsorbed and removed in the biological activated carbon tower, they undergo some form change by living organisms by passing through the biological activated carbon tower, and the reverse osmosis membrane separation device or ion exchange device in the latter stage It is considered that the TOC concentration was stabilized at a low value because the substance was changed to a removable substance by the above method.
【００５５】なお、生物活性炭塔の入口の残留塩素濃度
を０ｍｇ／Ｌとした比較例２では、生物活性炭塔内での
菌体の増殖が著しく、１日当りの圧力損失の増加が大き
かった。In Comparative Example 2 in which the residual chlorine concentration at the inlet of the biological activated carbon tower was 0 mg / L, the growth of the cells in the biological activated carbon tower was remarkable, and the increase in the pressure loss per day was large.
【００５６】[0056]
【発明の効果】以上詳述した通り、本発明の超純水製造
装置及び超純水製造方法によれば、ＴＯＣ濃度が著しく
低い、不純物の問題のない高純度な超純水を長期に亘り
安定に製造することができる。本発明の超純水製造装置
及び超純水製造方法により製造された超純水は、超ＬＳ
Ｉチップ洗浄水として、良好な洗浄効果を得ることがで
きる。As described above in detail, according to the ultrapure water production apparatus and the ultrapure water production method of the present invention, high purity ultrapure water having a very low TOC concentration and no problem of impurities can be produced for a long time. It can be manufactured stably. The ultrapure water produced by the ultrapure water production apparatus and the ultrapure water production method of the present invention is super LS
A good cleaning effect can be obtained as the I-chip cleaning water.
【図１】本発明の超純水製造装置の実施の形態を示す系
統図である。FIG. 1 is a system diagram showing an embodiment of an ultrapure water production apparatus according to the present invention.
【図２】従来の超純水製造装置を示す系統図である。FIG. 2 is a system diagram showing a conventional ultrapure water production apparatus.
【図３】実験例１の結果を示すグラフである。FIG. 3 is a graph showing the results of Experimental Example 1.
【図４】実験例２の結果を示すグラフである。FIG. 4 is a graph showing the results of Experimental Example 2.
１ 前処理システム ２ 一次純水系システム ３ サブシステム 1 Pretreatment system 2 Primary pure water system 3 Subsystem
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０２Ｆ 1/50 Ｃ０２Ｆ 1/50 ５３１Ｒ ５５０ ５５０Ｌ ５６０ ５６０Ｄ ５６０Ｅ ５６０Ｈ ５６０Ｚ 1/76 1/76 Ａ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (Reference) C02F 1/50 C02F 1/50 531R 550 550L 560 560D 560E 560H 560Z 1/76 1/76 A
Claims (6)
ステムの処理水を処理するサブシステムとを有する超純
水製造装置において、 該一次純水系システムに生物活性炭塔が設けられてお
り、 該生物活性炭塔は、制限された量の抗菌剤の存在下に原
水を処理して、原水中の有機物を生物的に分解するもの
であることを特徴とする超純水製造装置。1. An ultrapure water production apparatus having a primary pure water system and a subsystem for treating treated water of the primary pure water system, wherein the primary pure water system is provided with a biological activated carbon tower, An apparatus for producing ultrapure water, wherein the biological activated carbon tower is configured to treat raw water in the presence of a limited amount of an antibacterial agent to biologically decompose organic substances in the raw water.
活性炭への菌体付着量が１０６個／ｇより少なくなるよ
うな量の抗菌剤の存在下に原水を処理することを特徴と
する超純水製造装置。2. The method of claim 1, and characterized by treating the raw water in the presence of an amount of an antimicrobial agent, such as cell adhesion amount to the activated carbon of the organism activated carbon column in is less than 10 6 cells / g Ultrapure water production equipment.
素系抗菌剤であり、前記生物活性炭塔に流入する水の残
留塩素濃度が０．５〜５ｍｇ／Ｌであることを特徴とす
る超純水製造装置。3. The method according to claim 1, wherein the antibacterial agent is a chlorine-based antibacterial agent, and a residual chlorine concentration of water flowing into the biological activated carbon tower is 0.5 to 5 mg / L. Ultrapure water production equipment.
サブシステムで処理する超純水製造方法において、 該一次純水系システムにおいて、原水を制限された量の
抗菌剤の存在下に生物活性炭塔に通水して原水中の有機
物を生物的に分解することを特徴とする超純水製造方
法。4. A method for producing ultrapure water in which raw water is treated in a primary pure water system and then processed in a subsystem, wherein the raw water is treated in the primary pure water system in the presence of a limited amount of an antibacterial agent. A method for producing ultrapure water, characterized in that organic water in raw water is biologically decomposed by passing water through the water.
活性炭への菌体付着量が１０６個／ｇより少なくなるよ
うな量の抗菌剤の存在下に原水を通水することを特徴と
する超純水製造方法。5. The method of claim 4, characterized in that passed through the raw water in the presence of an amount of an antimicrobial agent, such as cell adhesion amount to the activated carbon of the organism activated carbon column in is less than 10 6 cells / g Ultrapure water production method.
素系抗菌剤であり、前記生物活性炭塔に通水する水の残
留塩素濃度が０．５〜５ｍｇ／Ｌであることを特徴とす
る超純水製造方法。6. The antibacterial agent according to claim 4, wherein the antibacterial agent is a chlorine-based antibacterial agent, and the concentration of residual chlorine in water passing through the biological activated carbon tower is 0.5 to 5 mg / L. Ultrapure water production method.
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