JP2514929B2 - Method for cleaning terminal reverse osmosis membrane device - Google Patents
Method for cleaning terminal reverse osmosis membrane deviceInfo
- Publication number
- JP2514929B2 JP2514929B2 JP61098179A JP9817986A JP2514929B2 JP 2514929 B2 JP2514929 B2 JP 2514929B2 JP 61098179 A JP61098179 A JP 61098179A JP 9817986 A JP9817986 A JP 9817986A JP 2514929 B2 JP2514929 B2 JP 2514929B2
- Authority
- JP
- Japan
- Prior art keywords
- reverse osmosis
- osmosis membrane
- pure water
- water
- cleaning
- 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.)
- Expired - Lifetime
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- Separation Using Semi-Permeable Membranes (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明はLSIや超LSIを生産する電子工業において、そ
の中間製品である半導体ウエハーまたはチップ（以下半
導体ウエハーという）の洗浄用の超純水を製造する目的
で末端に設置される逆浸透膜装置の洗浄方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention is ultrapure water for cleaning semiconductor wafers or chips (hereinafter referred to as semiconductor wafers), which are intermediate products in the electronic industry that produces LSIs and VLSIs. The present invention relates to a method for cleaning a reverse osmosis membrane device installed at the end for the purpose of manufacturing.
〈従来の技術〉 LSIや超LSIを生産する電子工業においては、その中間
製品である半導体ウエハーの洗浄にあたり、その歩留ま
りを向上させるために、イオンの量および微粒子の量を
ppbオーダーまで減少させるだけでなく、生菌数を10-1
個/mlまで減少させた、いわゆる超純水を必要とする。<Prior art> In the electronic industry that produces LSIs and VLSIs, the amount of ions and the amount of fine particles are increased in order to improve the yield when cleaning semiconductor wafers that are intermediate products
Not only to reduce to ppb order, but also to reduce the viable cell count to 10 -1
It requires so-called ultrapure water, reduced to pieces / ml.
従って従来ではかかる超純水を製造するにあたり、原
水を凝集沈殿装置、砂濾過器、活性炭濾過器、２床３塔
式純水製造装置、逆浸透膜装置、紫外線照射装置、混床
式ポリシャー等を組み合わせた一次側給水製造装置で可
能な限り高純度の純水を製造し、そして半導体ウエハー
を洗浄する直前で当該純水を更に超濾過膜（UF膜）装置
で処理し、いわゆる超純水を得、洗浄水として供してい
る。Therefore, conventionally, in producing such ultrapure water, raw water is coagulated and settled, a sand filter, an activated carbon filter, a two-bed three-column pure water production device, a reverse osmosis membrane device, an ultraviolet irradiation device, a mixed bed polisher, etc. The pure water of the highest possible purity is manufactured by the primary side water supply manufacturing device that combines the above, and the pure water is further processed by the ultrafiltration membrane (UF membrane) device immediately before cleaning the semiconductor wafer. Is used as washing water.
ところが最近になって製品の歩留まりを決定する要因
の一つにT.O.Cの量も少なければ少ない程、製品の歩留
まりが向上すると言われ、イオン量、微粒子量、生菌数
に加えてT.O.Cもその管理の対象となっている。However, recently, one of the factors that determines the product yield is said to be that the smaller the TOC amount is, the higher the product yield is.In addition to the ion amount, fine particle amount, viable cell count, TOC is also controlled. Is subject to.
水中の含まれるT.O.Cは逆浸透膜装置で除去可能であ
り、前述の一次側給水製造装置に逆浸透膜装置が用いら
れている場合は、当該逆浸透膜装置の上流側の水中に含
まれるT.O.Cは当該逆浸透膜装置で除去できるので問題
ない。しかしながら一次側給水製造装置の後段には種々
の装置が設置されるのが普通であり、当該後段装置から
T.O.Cが溶出し、かつ当該溶出したT.O.Cは比較的低分子
の有機物に起因するもので、前述した超濾過膜装置では
そのほとんどが除去できない。The TOC contained in the water can be removed by the reverse osmosis membrane device, and when the reverse osmosis membrane device is used in the above-mentioned primary side water supply manufacturing device, the TOC contained in the water on the upstream side of the reverse osmosis membrane device. Since it can be removed by the reverse osmosis membrane device, there is no problem. However, it is usual that various devices are installed after the primary side water supply manufacturing device.
TOC is eluted, and the eluted TOC is caused by a relatively low molecular weight organic substance, and most of it cannot be removed by the above-mentioned ultrafiltration membrane device.
従って半導体ウエハーを洗浄する直前、換言すれば超
純水を製造する末端で逆浸透膜装置で処理することが考
えられる。Therefore, it is conceivable to treat the semiconductor wafer with a reverse osmosis membrane device immediately before cleaning, in other words, at the end where ultrapure water is produced.
また当該逆浸透膜装置に用いられる逆浸透膜として
は、酢酸セルローズ系膜、ポリアミド系膜、あるいはポ
リアミド系とポリスルホン系の複合膜等が考えられる
が、酢酸セルローズ系膜は膜基材そのものが菌類の栄養
源となり、菌類が極めて繁殖し易いという点で一次系給
水処理装置から得られる純水の透過処理には適していな
く、ポリアミド系あるいはポリアミド系とポリスルホン
系の複合膜が用いられる。The reverse osmosis membrane used in the reverse osmosis membrane device may be a cellulose acetate membrane, a polyamide membrane, a polyamide-polysulfone composite membrane, or the like. It is not suitable for the permeation treatment of pure water obtained from the primary water supply treatment device in that it becomes a nutrient source of the above, and the fungi are very easily proliferated, and a polyamide type or a polyamide type and polysulfone type composite membrane is used.
一方超純水製造装置の末端に逆浸透膜装置を用いた場
合、以下のような問題点が生ずる。On the other hand, when a reverse osmosis membrane device is used at the end of the ultrapure water production system, the following problems occur.
すなわち逆浸透膜装置はその構造上、一般細菌が発生
し易く、従って定期的に殺菌処理を実施する必要があ
る。That is, due to the structure of the reverse osmosis membrane device, general bacteria are liable to be generated, and therefore it is necessary to regularly perform sterilization treatment.
当該殺菌処理は通常一週間に一回の割合で、0.5〜１
％の過酸化水素溶液で一時間程度、逆浸透膜装置を洗浄
するものであるが、このような殺菌膜装置を洗浄するも
のであるが、このような殺菌処理を実施しないと、逆浸
透膜の膜面に繁殖する一般細菌のために透過水量が低下
したり、更に透過水に多量の生菌が漏洩することとな
り、従って超純水を製造する末端に逆浸透膜装置を用い
るかぎり、当該細菌処理を省略することができない。The sterilization is usually performed once a week at 0.5-1.
% Hydrogen peroxide solution is used to wash the reverse osmosis membrane device for about 1 hour. This is for cleaning such a sterilization membrane device. The amount of permeated water decreases due to general bacteria that propagate on the membrane surface, and a large amount of viable bacteria leaks into the permeated water. Therefore, unless a reverse osmosis membrane device is used at the end for producing ultrapure water, Bacterial treatment cannot be omitted.
〈発明が解決しようとする問題点〉 ところがこのような細菌処理をすると、その処理後の
洗浄に多量の純水を用いないと透過水の比抵抗が上昇し
ないという問題が生ずる。例えば前記殺菌処理後に比抵
抗17.5MΩ−cm（25℃）以上の純水で洗浄する場合、透
過水中に過酸化水素が全く存在していないにもかかわら
ず透過水の比抵抗が供給洗浄水のそれと同等になるのに
24時間以上も要する。<Problems to be Solved by the Invention> However, such a bacterial treatment causes a problem that the specific resistance of permeated water does not increase unless a large amount of pure water is used for washing after the treatment. For example, when washing with pure water having a specific resistance of 17.5 MΩ-cm (25 ° C.) or more after the sterilization treatment, the specific resistance of the permeated water is the same as that of the supplied cleaning water even though hydrogen peroxide is not present in the permeated water at all. To be the same
It takes more than 24 hours.
当該洗浄用の純水は前述したごとく種々の装置によっ
て高コストをかけて製造した純水であり、これを末端逆
浸透膜装置の洗浄のために多量に用いることは甚だ不経
済である。The pure water for cleaning is pure water produced by various devices at high cost as described above, and it is very uneconomical to use a large amount of this pure water for cleaning the terminal reverse osmosis membrane device.
本発明は従来技術におけるかかる問題点に鑑みてなさ
れたものであり、その目的とするところは末端逆浸透膜
装置を過酸化水素溶液で殺菌処理した後の洗浄におい
て、可及的少量の洗浄水によって効果的に洗浄するとこ
ろにある。The present invention has been made in view of such problems in the prior art, and an object thereof is to wash a terminal reverse osmosis membrane device after sterilization treatment with a hydrogen peroxide solution, in a wash water as small as possible. It is in the place of effective cleaning.
〈問題点を解決するための手段〉 本発明は一次側給水製造装置で得られる純水を再度透
過処理する末端逆浸透膜装置において、当該逆浸透膜装
置に用いる逆浸透膜としてポリアミド系あるいはポリア
ミド系とポリスルホン系の複合膜を用い、当該逆浸透膜
を過酸化水素溶液で殺菌処理した後、アルカリ性純水、
45℃以上の加熱純水、アルコール液から選択される少な
くとも一種類の洗浄液で洗浄することを特徴とする末端
逆浸透膜装置の洗浄方法である。<Means for Solving Problems> The present invention relates to a terminal reverse osmosis membrane device for re-permeating pure water obtained in a primary side water supply production device, wherein a polyamide or polyamide is used as the reverse osmosis membrane used in the reverse osmosis membrane device. System and polysulfone type composite membrane, after sterilizing the reverse osmosis membrane with hydrogen peroxide solution, alkaline pure water,
A method for cleaning a terminal reverse osmosis membrane device, which comprises cleaning with at least one cleaning solution selected from pure water heated at 45 ° C. or higher and an alcohol solution.
〈作用〉 本発明者等は逆浸透膜装置を過酸化水素溶液で殺菌処
理した後の洗浄において、その透過水の比抵抗が中々上
昇しない原因を種々検討した結果、過酸化水素原液にあ
らかじめ添加されている分解抑制剤である陰イオンが、
逆浸透膜構成分子中のアミン基にイオン交換され、この
陰イオンが洗浄中に徐々に加水分解されて透過水中に漏
洩するのがその主な原因であることを知見した。<Function> The inventors of the present invention have conducted various studies on the reason why the specific resistance of the permeated water does not rise in the cleaning after sterilizing the reverse osmosis membrane device with the hydrogen peroxide solution, and added it to the hydrogen peroxide stock solution in advance. Anion, which is a decomposition inhibitor that is used,
It was found that the main cause is that the anion is ion-exchanged with an amine group in the molecule constituting the reverse osmosis membrane, and this anion is gradually hydrolyzed during the washing and leaks into the permeated water.
過酸化水素原液には、過酸化水素が自己分解するのを
防止するために、リン酸、リン酸塩、ピロリン酸、ピロ
リン酸塩等の分解抑制剤があらかじめ添加されており、
またLSIや超LSIを生産する電子工業等で用いられる比較
的高純度の過酸化水素原液においても前記抑制剤は例外
なく添加されている。In order to prevent hydrogen peroxide from self-decomposing in the hydrogen peroxide stock solution, a decomposition inhibitor such as phosphoric acid, phosphate, pyrophosphate or pyrophosphate is added in advance,
The inhibitor is also added without exception to a relatively high-purity hydrogen peroxide stock solution used in the electronics industry for producing LSI and VLSI.
このような過酸化水素原液を高純度純水で希釈して0.
5〜１％の過酸化水素溶液を調整し、当該溶液に逆浸透
膜を浸漬したり、あるいは当該溶液を逆浸透膜に通過さ
せたりする殺菌処理を行うと、逆浸透膜の材質がポリア
ミド系膜あるいはポリアミド系膜とポリスルホン系の複
合膜の場合は、以下のような現象が生ずる。Dilute such a hydrogen peroxide stock solution with high-purity pure water to prepare a solution.
When a 5 to 1% hydrogen peroxide solution is prepared and the reverse osmosis membrane is immersed in the solution or sterilized by passing the solution through the reverse osmosis membrane, the material of the reverse osmosis membrane is polyamide type. In the case of a membrane or a polyamide-based membrane and a polysulfone-based composite membrane, the following phenomena occur.
すなわち前述の分解抑制剤であるリン酸、ピロリン酸
等の陰イオンがポリアミド系膜の分子構造中に僅かに存
在するアミン基にイオン交換され、当該陰イオンが膜構
成分子中に一旦保持される。なお上記のアミン基は、弱
塩基性陰イオン交換樹脂に付加されている交換基とほぼ
同一種類のものである。That is, anions such as phosphoric acid and pyrophosphate, which are the above-mentioned decomposition inhibitors, are ion-exchanged with amine groups that are slightly present in the molecular structure of the polyamide-based membrane, and the anions are once retained in the membrane constituent molecules. . The amine group is of the same type as the exchange group added to the weakly basic anion exchange resin.
次いで殺菌処理後に高純度純水で洗浄すると、前記ア
ミン基にイオン交換された例えばリン酸イオンが加水分
解反応によりリン酸を生じ、これが透過水中に徐々に漏
洩することとなる。Then, when it is washed with high-purity pure water after the sterilization treatment, for example, phosphate ions ion-exchanged with the amine groups generate phosphoric acid by a hydrolysis reaction, and this gradually leaks into permeated water.
この現象は、塩形にした弱酸性陰イオン交換樹脂を純
水で洗浄する際に、その洗浄排水に微量の酸がいつまで
も漏洩する場合とよく似ている。This phenomenon is very similar to the case where a trace amount of acid leaks forever to the washing wastewater when the salt-form weakly acidic anion exchange resin is washed with pure water.
逆浸透膜の構成分子中に存在するアミン基は、弱塩基
性陰イオン交換樹脂と比較すると極めて少なく、加水分
解反応によって透過水中に漏洩する例えばリン酸イオン
のごとき陰イオンも極めて少量である。The amine groups present in the constituent molecules of the reverse osmosis membrane are extremely small compared to weakly basic anion exchange resins, and the anions such as phosphate ions leaking into the permeated water due to the hydrolysis reaction are also extremely small.
なお従来からこのような現象が生じていたとしてもそ
の量が極めて少量なので看過されていたものと思われ
る。Even if such a phenomenon has occurred, it is considered that it has been overlooked because it is extremely small.
しかしながら本発明が対象とする末端逆浸透膜装置
は、過酸化水素溶液による殺菌処理後に、理論純水に近
い比抵抗17.5MΩ−cm（25℃）以上の高純度純水で洗浄
するので、極微量の陰イオンと言えどもこれが漏洩する
と透過水の比抵抗が供給洗浄水のそれと同等とならず前
述したごとく洗浄水を多量に消費することとなる。However, the terminal reverse osmosis membrane device targeted by the present invention is washed with high-purity pure water having a specific resistance of 17.5 MΩ-cm (25 ° C.) or more close to theoretical pure water after sterilization treatment with a hydrogen peroxide solution. Even if a small amount of anions are leaked, the specific resistance of the permeated water will not be the same as that of the supplied wash water, and a large amount of wash water will be consumed as described above.
従って過酸化水素溶液による殺菌処理後に可及的速や
かに前記アミン基に保持されている陰イオンを除去して
しまえば洗浄水を多量に消費することがない。Therefore, if the anions held by the amine groups are removed as soon as possible after the sterilization treatment with the hydrogen peroxide solution, a large amount of washing water is not consumed.
本発明におけるアルカリ性純水、45℃以上の加熱純
水、アルコール液は、いずれもアミン基に保持されてい
る陰イオンを可及的速やかに除去するためのものであ
る。The alkaline pure water, the pure water heated at 45 ° C. or higher, and the alcohol liquid in the present invention are all for removing anions held by amine groups as quickly as possible.
すなわちアルカリ性純水はアミン基にイオン交換され
ている陰イオンを速やかに水酸イオンと置換させる作用
を有し、この作用は塩型の弱塩基性陰イオン交換樹脂を
アルカリで再生する場合と原理的には同じである。In other words, alkaline pure water has the action of rapidly replacing the anions that have been ion-exchanged for amine groups with hydroxide ions, and this action is the same as in the case of regenerating salt-type weakly basic anion exchange resins with alkali. Are the same.
また45℃以上の加熱純水は、前述の加水分解反応その
ものを加速する作用を有しており、45℃以上の加熱純水
を接触させることにより可及的速やかに加水分解反応を
進めてアミン基にイオン交換されている陰イオンを早期
に洗い出すものである。Further, the pure water heated at 45 ° C or higher has an action of accelerating the hydrolysis reaction itself, and by bringing the pure water heated at 45 ° C or higher into contact, the hydrolysis reaction proceeds as quickly as possible. The anions that have been ion-exchanged with the base are washed out at an early stage.
またアルコール液は前記アミン基に対するリン酸等の
陰イオンの吸着選択性を変化させる作用を有しており、
逆浸透膜にアルコール液を接触させることにより速やか
に前記陰イオンを離脱させることができる。Further, the alcohol liquid has a function of changing the adsorption selectivity of anions such as phosphoric acid with respect to the amine group,
The anion can be promptly released by bringing the reverse osmosis membrane into contact with an alcohol solution.
本発明におけるアルカリ性純水、45℃以上の加熱純
水、アルコール液の作用は上述したごとくであり、過酸
化水素溶液で殺菌処理した後、これらの洗浄液から選択
される少なくとも一種類の洗浄液で洗浄することにより
本発明の目的を達することができる。なお必要に応じ上
記洗浄液の内二種類以上を使用しても差し支えない。The action of the alkaline pure water, the pure water heated at 45 ° C. or higher, and the alcohol solution in the present invention is as described above, and after sterilization treatment with a hydrogen peroxide solution, cleaning with at least one cleaning solution selected from these cleaning solutions By doing so, the object of the present invention can be achieved. If necessary, two or more kinds of the above cleaning solutions may be used.
本発明に用いるアルカリ性純水としてはpH9〜11の範
囲が好ましく、通常はpH10前後のものを用いるとよい。
なおpHが９以下ではアルカリ量が不足し、アミン基にイ
オン交換した陰イオンを早期に水酸イオンと交換する作
用が低下し、またpHが11以上では膜そのものが劣化する
のでいずれも好ましくない。The alkaline pure water used in the present invention preferably has a pH range of 9 to 11, and it is generally preferable to use one having a pH of around 10.
When the pH is 9 or less, the amount of alkali is insufficient, the action of exchanging anions ion-exchanged for amine groups with hydroxide ions is reduced, and when the pH is 11 or more, the membrane itself is deteriorated. .
また本発明に用いる45℃以上の加熱純水は、温度が45
℃〜60℃が好ましく、通常は50℃前後の加熱純水を用い
るとよい。なお45℃以下では前述した加水分解反応を加
速する作用が低下するので好ましくなく、また60℃以上
の高温では熱により膜そのものが劣化するので好ましく
ない。Further, the heated pure water of 45 ° C. or higher used in the present invention has a temperature of 45
C. to 60.degree. C. is preferable, and heated pure water at about 50.degree. C. is usually used. If the temperature is 45 ° C. or lower, the above-mentioned action of accelerating the hydrolysis reaction is lowered, which is not preferable, and if the temperature is higher than 60 ° C., the film itself is deteriorated by heat, which is not preferable.
更に本発明に用いるアルコール液としては、メチルア
ルコール、エチルアルコール、プロピルアルコール等の
低級アルコールが好ましく、その濃度は少なくとも30％
以上が望ましい。なお30％以下の濃度の薄いアルコール
液では前述した陰イオンの吸着選択性を変化させること
ができず、本発明の目的を達することが困難となるので
好ましくない。また30％以上の濃度であれば、たとえ10
0％のアルコール液を用いても本発明の効果は達成でき
るが、濃度をあまり高くするといたずらに処理薬品費を
増加させることとなるので、通常は50％前後のアルコー
ル液を用いるとよい。Further, as the alcohol liquid used in the present invention, lower alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol are preferable, and the concentration thereof is at least 30%.
The above is desirable. A thin alcohol solution having a concentration of 30% or less cannot change the adsorption selectivity of the anion described above, and it is difficult to attain the object of the present invention, which is not preferable. If the concentration is 30% or more, even 10
Although the effect of the present invention can be achieved by using an alcohol solution of 0%, if the concentration is too high, the treatment chemical cost will be unnecessarily increased. Therefore, it is usually preferable to use an alcohol solution of about 50%.
本発明においては末端逆浸透膜装置を常法により過酸
化水素溶液で殺菌処理した後、上述した洗浄液の少なく
とも一種類の洗浄液を逆浸透膜装置に供給して、当該洗
浄液の液量として25l/エレメント〜30l/エレメントを透
過処理し、次いで高純度純水にて通常の洗浄を実施すれ
ばよく、本発明の洗浄が約一時間、最終の高純度純水に
よる洗浄が約30分の合計を約1.5時間という極めて短時
間で17MΩ−cm以上の高純度の透過水が得られる。In the present invention, after sterilizing the terminal reverse osmosis membrane device with a hydrogen peroxide solution by a conventional method, at least one kind of the above-mentioned cleaning liquid is supplied to the reverse osmosis membrane device, and the volume of the cleaning liquid is 25 l / Permeation treatment of the element to 30 l / element, followed by normal cleaning with high-purity pure water, the cleaning of the present invention takes about 1 hour, and the final cleaning with high-purity pure water takes about 30 minutes. Highly pure permeated water of 17 MΩ-cm or more can be obtained in an extremely short time of about 1.5 hours.
以下に本発明の実施態様を説明する。 Embodiments of the present invention will be described below.
第１図は本発明の実施態様の一例を示すフローの説明
図であり、点線は殺菌および洗浄ラインを示しており、
また一点鎖線内はユースポイントを示している。FIG. 1 is an explanatory view of a flow showing an example of an embodiment of the present invention, in which a dotted line shows a sterilization and cleaning line,
In addition, the use points are shown in the chain lines.
超純水を製造する場合は、一次側給水製造装置で製造
された一次側純水１を一旦純水槽２に貯留し、当該純水
を混床式ポリシャー３、紫外線照射装置４、末端逆浸透
膜装置５で処理し、一次側純水１中に残留するイオン、
微粒子、生菌、T.O.C等を可及的に除去して、いわゆる
超純水を製造する。なお末端逆浸透膜装置５の透過水で
ある超純水はユースポイント配管６によって、ユースポ
イント７まで移送し、ここで必要な超純水を半導体ウエ
ハーの洗浄水として使用し、残余の超純水は純水槽２に
循環する。In the case of producing ultrapure water, the primary side pure water 1 produced by the primary side water supply production device is temporarily stored in a pure water tank 2, and the pure water is mixed with the mixed bed polisher 3, the ultraviolet irradiation device 4, and the terminal reverse osmosis. Ions that have been treated in the membrane device 5 and remain in the primary side pure water 1,
So-called ultrapure water is produced by removing fine particles, viable bacteria, TOC, etc. as much as possible. The ultrapure water, which is the permeated water of the terminal reverse osmosis membrane device 5, is transferred to the use point 7 through the use point pipe 6, and the ultrapure water required there is used as the cleaning water for the semiconductor wafer, and the remaining ultrapure water is used. Water circulates in the pure water tank 2.
また末端逆浸透膜装置５の非透過水も通常は非透過水
循環配管８により純水槽２に戻される。なお第１図では
混床式ポリシャー３が前段に紫外線照射装置４が後段に
設置されているが、場合によっては紫外線照射装置４が
前段に混床式ポリシャー３が後段になることもある。た
だし末端逆浸透膜装置５は必ず超純水製造工程の末端に
設置される。The non-permeated water of the terminal reverse osmosis membrane device 5 is also usually returned to the pure water tank 2 through the non-permeated water circulation pipe 8. In FIG. 1, the mixed-bed polisher 3 is installed in the front stage and the ultraviolet irradiation device 4 is installed in the rear stage, but in some cases, the ultraviolet irradiation device 4 may be installed in the front stage and the mixed-bed polisher 3 may be installed in the rear stage. However, the terminal reverse osmosis membrane device 5 is always installed at the end of the ultrapure water production process.
次に末端逆浸透膜装置５の殺菌処理は次の通りであ
る。Next, the sterilization treatment of the terminal reverse osmosis membrane device 5 is as follows.
過酸化水素原液を末端逆浸透膜装置５の供給水である
高純度純水で希釈し、0.5〜１％の過酸化水素溶液を過
酸化水素溶液貯槽９に調整し、当該過酸化水素溶液を末
端逆浸透膜装置に供給する。The hydrogen peroxide stock solution is diluted with high-purity pure water that is the feed water for the terminal reverse osmosis membrane device 5, and a 0.5 to 1% hydrogen peroxide solution is adjusted in the hydrogen peroxide solution storage tank 9, and the hydrogen peroxide solution is Supply to the terminal reverse osmosis membrane device.
供給方法としては以下の通りである。 The supply method is as follows.
まず透過水側を閉塞して主に逆浸透膜の表面を過酸化
水素溶液で洗浄し、その過酸化水素排液を非透過水側か
らブローする。当該工程を約30分程度行った後、次いで
透過水側も開口し、過酸化水素溶液を逆浸透膜に通過さ
せ、非透過水側および透過水側から過酸化水素排液を約
30分間ブローする。なお場合によっては透過水側から流
出する過酸化水素排液を循環回収することもできる。First, the permeated water side is closed, the surface of the reverse osmosis membrane is mainly washed with a hydrogen peroxide solution, and the hydrogen peroxide drainage is blown from the non-permeated water side. After performing this step for about 30 minutes, the permeate side is then opened, the hydrogen peroxide solution is passed through the reverse osmosis membrane, and the hydrogen peroxide drainage solution is discharged from the non-permeate side and the permeate side.
Blow for 30 minutes. Depending on the case, the hydrogen peroxide waste liquid flowing out from the permeated water side can be circulated and collected.
このように過酸化水素溶液による殺菌を行った後、本
発明における洗浄液で末端逆浸透膜装置５を洗浄する。After sterilizing with the hydrogen peroxide solution in this way, the terminal reverse osmosis membrane device 5 is washed with the washing liquid of the present invention.
すなわち末端逆浸透膜装置５の供給水である高純度純
水を洗浄液槽10に貯留し、これにカ性ソーダを添加して
pH10前後のアルカリ性純水を調整し、当該アルカリ性純
水を末端逆浸透膜装置５に供給する。That is, high-purity pure water, which is the feed water for the terminal reverse osmosis membrane device 5, is stored in the cleaning liquid tank 10, and caustic soda is added to this.
The alkaline pure water having a pH of about 10 is adjusted, and the alkaline pure water is supplied to the terminal reverse osmosis membrane device 5.
供給方法としては洗浄液の全量を逆浸透膜に通過させ
るが、場合によってはその一部を非透過水側からブロー
しても差し支えない。なお当該洗浄の所要時間は約一時
間前後で充分である。As a supply method, the entire amount of the cleaning liquid is passed through the reverse osmosis membrane, but in some cases, a part thereof may be blown from the non-permeate side. About one hour is sufficient for the cleaning.
このようなアルカリ性純水による洗浄が終了した後、
紫外線照射装置４後の高純度純水を末端逆浸透膜装置５
に供給し、透過水の比抵抗が供給洗浄水のそれと同等に
上昇するまでその非透過水と透過水をブローし、透過水
の比抵抗が供給洗浄水のそれと同等に上昇した後、非透
過水を非透過水循環配管８により純水槽２に戻すととも
に、透過水をユースポイント配管６に通流させる。After such cleaning with alkaline pure water is completed,
The high-purity pure water after the ultraviolet irradiation device 4 is subjected to the terminal reverse osmosis membrane device 5
Blow the non-permeate and permeate until the specific resistance of the permeated water rises to the same level as that of the supplied wash water, and the specific resistance of the permeated water rises to the same as that of the supplied wash water, then The water is returned to the pure water tank 2 through the non-permeate water circulation pipe 8 and the permeate is allowed to flow through the use point pipe 6.
なお前述したごとく本発明の洗浄液で洗浄を行うと透
過水の比抵抗の上昇は極めて速くなり、通常30分以内で
透過水の比抵抗が供給洗浄水のそれと同等となるので短
時間で透過水をユースポイント配管６に通流させること
ができる。As described above, when the cleaning liquid of the present invention is used for cleaning, the increase in the specific resistance of the permeated water is extremely fast, and the specific resistance of the permeated water is usually equal to that of the supplied cleaning water within 30 minutes, so that the permeated water can be obtained in a short time. Can be passed through the use point pipe 6.
また本実施態様では洗浄液としてアルカリ性純水を用
いたが、45℃以上の加熱純水あるいはアルコール液を洗
浄液として用いてもその効果はほとんど同じである。Although alkaline pure water is used as the cleaning liquid in this embodiment, the same effect can be obtained by using pure water heated at 45 ° C. or higher or an alcohol liquid as the cleaning liquid.
〈効果〉 以上説明したごとく、本発明は末端逆浸透膜装置に用
いる逆浸透膜としてポリアミド系あるいはポリアミド系
とポリスルホン系の複合膜を用い、当該逆浸透膜を過酸
化水素溶液で殺菌処理した後、アルカリ性純水、45℃以
上の加熱純水、アルコール液から選択される少なくとも
一種類の洗浄液で洗浄することにより、透過水の比抵抗
上昇までの時間を飛躍的短時間とすることができ、洗浄
のために要する高純度純水の使用量を大幅に削減するこ
とができる。<Effects> As described above, the present invention uses a polyamide-based or polyamide-based and polysulfone-based composite membrane as the reverse osmosis membrane used in the terminal reverse osmosis membrane device, and after sterilizing the reverse osmosis membrane with a hydrogen peroxide solution. By cleaning with at least one kind of cleaning liquid selected from alkaline pure water, heated pure water of 45 ° C. or higher, and alcohol liquid, the time until the specific resistance of the permeated water increases can be dramatically shortened. The amount of high-purity pure water required for cleaning can be significantly reduced.
以下に本発明の効果を明確とするために実施例を説明
する。Examples will be described below to clarify the effects of the present invention.
実施例 ポリアミド系とポリスルホン系の複合膜である日東電
工（株）製NTR−7197モジュール二本を装着した末端逆
浸透膜装置を用いて、以下の実験を行った。Example The following experiment was performed using a terminal reverse osmosis membrane device equipped with two NTR-7197 modules manufactured by Nitto Denko Corporation, which are composite membranes of polyamide type and polysulfone type.
すなわち１％の過酸化水素溶液を40l調整し、当該溶
液を40l/Hの流速で末端逆浸透膜装置に供給し、まず非
透過水側のみから過酸化水素溶液を30分間流出させて、
主に逆浸透膜の膜面を洗浄し、次いで透過水側からも過
酸化水素溶液を流出させることにより逆浸透膜に過酸化
水素溶液を通過させ、この処理を30分間行った。That is, 40 l of a 1% hydrogen peroxide solution was prepared, and the solution was supplied to the terminal reverse osmosis membrane device at a flow rate of 40 l / H, and first, the hydrogen peroxide solution was allowed to flow out only from the non-permeate side for 30 minutes,
The membrane surface of the reverse osmosis membrane was mainly washed, and then the hydrogen peroxide solution was allowed to pass through the reverse osmosis membrane by letting the hydrogen peroxide solution also flow out from the permeate side, and this treatment was carried out for 30 minutes.
このような過酸化水素溶液による殺菌処理後に、pH10
のアルカリ性純水、温度50℃の加熱純水、50％のエチル
アルコール液の洗浄液それぞれについて以下の条件で洗
浄した。After sterilization with such a hydrogen peroxide solution, pH 10
Each of the alkaline pure water, the heated pure water at a temperature of 50 ° C. and the cleaning solution of a 50% ethyl alcohol solution was washed under the following conditions.
すなわち40lのpH10のアルカリ性純水を40l/Hの流速で
末端逆浸透膜装置に供給し、その全量を透過水側に流出
させた。なお温度50℃の加熱純水およびアルコール液の
場合もその液量と供給方法は同様である。このような洗
浄液による洗浄後、比抵抗17.5MΩ−cmの高純度純水を1
600l/Hで末端逆浸透膜に供給し、1000l/Hの非透過水と6
00l/Hの透過水を得たところ、pH10のアルカリ性純水、
温度50℃の加熱純水、アルコール液のいずれの洗浄液の
場合も、透過水の比抵抗が17.5MΩ−cmに達する時間は3
0分であった。That is, 40 l of alkaline pure water having a pH of 10 was supplied to the terminal reverse osmosis membrane device at a flow rate of 40 l / H, and the whole amount was allowed to flow to the permeate side. In the case of heated pure water and alcohol liquid having a temperature of 50 ° C., the liquid amount and the supplying method are the same. After cleaning with such a cleaning liquid, pure water with a specific resistance of 17.5 MΩ-cm
It is supplied to the terminal reverse osmosis membrane at 600 l / H, and 1000 l / H of impermeable water and 6
When we obtained permeated water of 00l / H, alkaline pure water of pH10,
The time required for the specific resistance of the permeated water to reach 17.5 MΩ-cm is 3 for both the cleaning solution heated at 50 ° C and pure water or alcohol.
It was 0 minutes.
一方比較のために、過酸化水素溶液による殺菌処理後
に本発明の洗浄液による洗浄を行わず、比抵抗17.5MΩ
−cmの高純度純水を同じように1600l/Hで末端逆浸透膜
に供給し、1000l/Hの非透過水と600l/Hの透過水を得た
ところ、透過水の比抵抗が17.5MΩ−cmに達する時間は2
5時間も要した。On the other hand, for comparison, after cleaning with the cleaning solution of the present invention was not performed after the sterilization treatment with a hydrogen peroxide solution, the specific resistance was 17.5 MΩ.
High-purity pure water of -cm was similarly supplied to the terminal reverse osmosis membrane at 1600 l / H to obtain 1000 l / H of non-permeated water and 600 l / H of permeated water, and the specific resistance of the permeated water was 17.5 MΩ. Time to reach −cm is 2
It took 5 hours.
第１図は本発明の実施態様の一例を示すフローの説明図
である。 １…一次側純水、２…純水槽 ３…混床式ポリシャー、４…紫外線照射装置 ５…末端逆浸透膜装置 ６…ユースポイント配管 ７…ユースポイント、８…非透過水循環配管 ９…過酸化水素溶液貯槽 10…洗浄液槽FIG. 1 is an explanatory diagram of a flow showing an example of an embodiment of the present invention. 1 ... Primary side pure water, 2 ... Pure water tank 3 ... Mixed bed polisher, 4 ... UV irradiation device 5 ... Terminal reverse osmosis membrane device 6 ... Use point piping 7 ... Use point, 8 ... Non-permeate water circulation piping 9 ... Peroxidation Hydrogen solution storage tank 10 ... Cleaning solution tank
Claims (1)
透過処理する末端逆浸透膜装置において、当該逆浸透膜
装置に用いる逆浸透膜としてポリアミド系あるいはポリ
アミド系とポリスルホン系の複合膜を用い、当該逆浸透
膜を過酸化水素溶液で殺菌処理した後、アルカリ性純
水、45C°以上の加熱純水、アルコール液から選択され
る少なくとも一種類の洗浄液で洗浄することを特徴とす
る末端逆浸透膜装置の洗浄方法。1. A terminal reverse osmosis membrane device for re-permeating pure water obtained in a primary side feed water producing apparatus, wherein a polyamide-based or polyamide-based polysulfone-based composite membrane is used as the reverse osmosis membrane used in the reverse osmosis membrane apparatus. After sterilizing the reverse osmosis membrane with a hydrogen peroxide solution, the reverse reverse osmosis membrane is washed with at least one kind of washing solution selected from alkaline pure water, heated pure water of 45 ° C. or higher, and alcohol solution. Method for cleaning osmotic membrane device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61098179A JP2514929B2 (en) | 1986-04-30 | 1986-04-30 | Method for cleaning terminal reverse osmosis membrane device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61098179A JP2514929B2 (en) | 1986-04-30 | 1986-04-30 | Method for cleaning terminal reverse osmosis membrane device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62254805A JPS62254805A (en) | 1987-11-06 |
| JP2514929B2 true JP2514929B2 (en) | 1996-07-10 |
Family
ID=14212798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61098179A Expired - Lifetime JP2514929B2 (en) | 1986-04-30 | 1986-04-30 | Method for cleaning terminal reverse osmosis membrane device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2514929B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5356651A (en) * | 1992-12-30 | 1994-10-18 | Pall Corporation | Manufacturing method for producing sterile milk using dynamic microfiltration |
| KR100205009B1 (en) * | 1996-04-17 | 1999-06-15 | 윤종용 | A video signal conversion device and a display device having the same |
| JP5077779B2 (en) * | 2009-07-03 | 2012-11-21 | 東洋紡績株式会社 | Method for producing composite semipermeable membrane and composite semipermeable membrane module |
| CN104548940B (en) * | 2015-01-13 | 2017-01-11 | 浙江工业大学 | Nanofiltration membrane pretreatment method capable of eliminating membrane separation oil-water emulsion |
| CN104801195A (en) * | 2015-04-30 | 2015-07-29 | 浙江农林大学 | Novel method for cleaning organic pollutants of reverse osmosis membrane and nanofiltration membrane |
| CN109289538B (en) * | 2017-07-25 | 2022-04-05 | 中国石油化工股份有限公司 | Method for on-line chemical cleaning of reverse osmosis membrane |
| CN109126466A (en) * | 2018-09-19 | 2019-01-04 | 山西晋煤天源化工有限公司 | Reverse osmosis on-line cleaning device |
-
1986
- 1986-04-30 JP JP61098179A patent/JP2514929B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62254805A (en) | 1987-11-06 |
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