JP5658908B2 - Method for producing purified water - Google Patents

Method for producing purified water Download PDF

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JP5658908B2
JP5658908B2 JP2010115112A JP2010115112A JP5658908B2 JP 5658908 B2 JP5658908 B2 JP 5658908B2 JP 2010115112 A JP2010115112 A JP 2010115112A JP 2010115112 A JP2010115112 A JP 2010115112A JP 5658908 B2 JP5658908 B2 JP 5658908B2
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exchange resin
anion exchange
chamber
ion exchange
edi
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JP2011240264A (en
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利夫 佐藤
利夫 佐藤
智暢 阿瀬
智暢 阿瀬
武志 野口
武志 野口
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Daicen Membrane Systems Ltd
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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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Description

本発明は、医療用及び工業用として適した精製水の製造方法に関する。   The present invention relates to a method for producing purified water suitable for medical use and industrial use.

人工透析液や注射液に使用される精製水は、微生物、エンドトキシンで汚染されていないものを用いる必要がある。   It is necessary to use purified water used for artificial dialysate and injection solution that is not contaminated with microorganisms and endotoxin.

特許文献１、２には、ＲＯ処理装置とＥＤＩ装置を組み合わせて、人工透析用水を製造するための装置と製造方法が記載されている。特許文献１には、ＥＤＩ処理水を逆浸透膜装置の入口に返送して循環させることが記載されている（段落００３９と図１参照）。   Patent Documents 1 and 2 describe a device and a manufacturing method for manufacturing artificial dialysis water by combining an RO treatment device and an EDI device. Patent Document 1 describes that EDI-treated water is returned to the inlet of the reverse osmosis membrane device and circulated (see paragraph 0039 and FIG. 1).

その他、半導体の製造工程のような産業用の製造ラインにおいて使用する洗浄水等に対しても、できるだけエンドトキシンや生菌等で汚染されていない清浄な精製水への需要が非常に大きい。   In addition, there is a great demand for clean purified water that is not contaminated with endotoxin, viable bacteria, and the like as much as possible for washing water used in industrial production lines such as semiconductor manufacturing processes.

特開２００７−２５２３９６号公報JP 2007-252396 A 特開２００７−２３７０６２号公報JP 2007-237062 A

本発明は、脱塩室に特定の陰イオン交換樹脂を備えた電気再生式脱イオン装置（ＥＤＩ装置）を用いることで、微生物やエンドトキシンの除去効果が向上された、医療用及び工業用精製水として適した精製水の製造方法を提供することを課題とする。   The present invention is a medical and industrial purified water having an improved effect of removing microorganisms and endotoxin by using an electric regeneration type deionization apparatus (EDI apparatus) having a specific anion exchange resin in a desalination chamber. It is an object of the present invention to provide a method for producing purified water suitable as the above.

本願発明は、課題の解決手段として、
電気再生式脱イオン装置（ＥＤＩ装置）を用いた精製水の製造方法であり、
前記ＥＤＩ装置が、イオン交換樹脂を備えたイオン交換室（脱塩室）、濃縮室、電極室（正及び負の電極室）を有するものであり、
前記イオン交換室内に充填されたイオン交換樹脂として少なくとも１種以上のＭＲ型の陰イオン交換樹脂を含む陰イオン交換樹脂を用いる、精製水の製造方法を提供する。 The present invention is a means for solving the problems,
A method for producing purified water using an electric regenerative deionization device (EDI device),
The EDI apparatus has an ion exchange chamber (desalting chamber) provided with an ion exchange resin, a concentration chamber, and electrode chambers (positive and negative electrode chambers).
Provided is a method for producing purified water using an anion exchange resin containing at least one MR type anion exchange resin as the ion exchange resin filled in the ion exchange chamber.

本発明の製造方法によれば、脱塩室にゲル形の陰イオン交換樹脂を充填した従来のＥＤＩ装置を用いた場合に比べて、除菌効果やエンドトキシン（ＥＴ）の除去効果を高めることができる。   According to the production method of the present invention, the sterilization effect and the endotoxin (ET) removal effect can be enhanced as compared with the case where a conventional EDI apparatus in which a desalination chamber is filled with a gel-type anion exchange resin is used. it can.

実施例１、比較例１の除菌効果を示すグラフ。The graph which shows the disinfection effect of Example 1 and Comparative Example 1. 実施例２、比較例２のＥＴの除去効果を示すグラフ。The graph which shows the removal effect of Example 2 and the comparative example 2 of ET. 実施例３、比較例３のイオン交換樹脂から脱離されたものの生菌数を示すグラフ。The graph which shows the number of viable bacteria of what was desorbed from the ion exchange resin of Example 3 and Comparative Example 3. 実施例４、比較例４のイオン交換樹脂から脱離されたもののＥＴ活性を示すグラフ。The graph which shows ET activity of what was desorbed from the ion exchange resin of Example 4 and Comparative Example 4. 実施例５、比較例５の処理水の電気伝導度を示すグラフ。The graph which shows the electrical conductivity of the treated water of Example 5 and Comparative Example 5. 実施例６、比較例６の処理水のｐＨを示すグラフ。The graph which shows pH of the treated water of Example 6 and Comparative Example 6. 参考例１の除菌効果を示すグラフ。The graph which shows the microbe elimination effect of the reference example 1. FIG. 参考例２のＥＴの除去効果を示すグラフ。The graph which shows the removal effect of ET of the reference example 2. 参考例３の除菌効果を示すグラフ。The graph which shows the microbe elimination effect of the reference example 3. 参考例４のＥＴの除去効果を示すグラフ。The graph which shows the removal effect of ET of the reference example 4.

＜ＥＤＩ装置＞
本発明の製造方法で用いるＥＤＩ装置は、イオン交換樹脂を備えたイオン交換室（脱塩室）内に充填された陰イオン交換樹脂として少なくとも1種以上のＭＲ（macro−reticular）型の陰イオン交換樹脂を含む陰イオン交換樹脂を用いることが従来技術と異なるものである。 <EDI device>
The EDI apparatus used in the production method of the present invention includes at least one MR (macro-reticular) type anion as an anion exchange resin filled in an ion exchange chamber (desalting chamber) provided with an ion exchange resin. The use of an anion exchange resin including an exchange resin is different from the prior art.

ＥＤＩ装置自体は汎用されているものであり、例えば、特許文献１、２に記載のもの、特開平１１−２４４８５３号公報、特開２００１−２３９２７０号公報、特開２００１−３５３４９８号公報、特開２００４−７４１０９号公報に記載のもののほか、市販のＥＤＩ装置である、ＥＤＩシステムシリーズ，商品名ＭＯＬＳＥＰ（登録商標）（ダイセン・メンブレン・システムズ（株）販売）等を用いることができる。
本発明を実施する際には、市販のＥＤＩ装置のイオン交換室（脱塩室）内に充填された陰イオン交換樹脂を少なくとも1種以上のＭＲ型の強塩基性陰イオン交換樹脂を含む陰イオン交換樹脂に替えることで対応できる。 The EDI apparatus itself is widely used. For example, those disclosed in Patent Documents 1 and 2, JP-A-11-244853, JP-A-2001-239270, JP-A-2001-353498, JP-A-2001-353498, In addition to what is described in Japanese Patent Application Publication No. 2004-74109, a commercially available EDI apparatus such as EDI system series, trade name MOLSEP (registered trademark) (sold by Daisen Membrane Systems Co., Ltd.) and the like can be used.
In carrying out the present invention, an anion exchange resin filled in an ion exchange chamber (desalting chamber) of a commercially available EDI apparatus is an anion containing at least one MR type strongly basic anion exchange resin. This can be done by switching to ion exchange resin.

ＥＤＩ装置で用いるＭＲ型の陰イオン交換樹脂は公知のものであり、ゲル形の陰イオン交換樹脂とは異なり、表面に細孔を有するものである。
ＭＲ型の陰イオン交換樹脂は市販されており、例えば、ダイヤイオン（登録商標）ＰＫシリーズ（三菱化成社製）、アンバーライト（登録商標）２００シリーズ（ローム＆ハース社製）、アンバーライト（登録商標）IRA900J、IRA904（オルガノ製）、アンバーリスト（登録商標）ＸＮシリーズ（ローム＆ハース社製）、ダウエックス（登録商標）ＭＳＣ−１（ダウケミカル社製）、レバチット（登録商標）ＳＰシリーズ（バイエル社製）が知られている。 MR-type anion exchange resins used in the EDI apparatus are known and have pores on the surface unlike gel-type anion exchange resins.
MR type anion exchange resins are commercially available. For example, Diaion (registered trademark) PK series (manufactured by Mitsubishi Kasei), Amberlite (registered trademark) 200 series (produced by Rohm & Haas), Amberlite (registered) Trademarks: IRA900J, IRA904 (manufactured by Organo), Amberlyst (registered trademark) XN series (manufactured by Rohm & Haas), Dowex (registered trademark) MSC-1 (manufactured by Dow Chemical Company), Lebatit (registered trademark) SP series ( Bayer) is known.

ＥＤＩ装置で用いるＭＲ型の陰イオン交換樹脂としては、マクロ孔とミクロ孔を有する強塩基性のものであり、前記マクロ孔が直径２〜２０μmの範囲の孔であり、ミクロ孔が直径２０〜３００ｎｍの範囲の孔であるものを有しているものが好ましい。前記マクロ孔の孔径測定およびミクロ孔の孔径測定は、それぞれ水銀圧入法による測定法と気体吸着法による測定法が用いられる。   The MR type anion exchange resin used in the EDI apparatus is a strongly basic resin having macropores and micropores. The macropores are pores having a diameter of 2 to 20 μm, and the micropores have a diameter of 20 to 20 mm. Those having pores in the range of 300 nm are preferred. For the measurement of the pore size of the macropores and the measurement of the pore size of the micropores, a measurement method using a mercury intrusion method and a measurement method using a gas adsorption method are used, respectively.

さらに本発明では、上記数値範囲内に含まれるものの内、下記の（I）及び（II）のＭＲ型の陰イオン交換樹脂がより好ましい。
（I）マクロ孔とミクロ孔を有する強塩基性のものであり、マクロ孔が直径２〜２０μmの範囲の孔であり、ミクロ孔が直径２０〜６０ｎｍ（好ましくは直径２８〜４４ｎｍ）（但し、全細孔容積の5.0〜95.0％の範囲にある孔径である）の範囲の孔であるものを有しており、イオン交換容量は、０．８〜１．５ｍｅｑ／ｍｌ湿潤樹脂）の範囲のもの。 Further, in the present invention, among those included in the above numerical range, the following (I) and (II) MR type anion exchange resins are more preferable.
(I) Strongly basic having macropores and micropores, macropores having a diameter of 2 to 20 μm, and micropores having a diameter of 20 to 60 nm (preferably a diameter of 28 to 44 nm) (provided that The pore diameter is in the range of 5.0 to 95.0% of the total pore volume), and the ion exchange capacity is in the range of 0.8 to 1.5 meq / ml wet resin) thing.

（II）マクロ孔とミクロ孔を有する強塩基性のものであり、マクロ孔が直径２〜２０μmの範囲の孔であり、ミクロ孔が直径３０〜３００ｎｍ（好ましくは直径４２〜２４０ｎｍ）（但し、全細孔容積の5.0〜95.0％の範囲にある孔径である）の範囲の孔であるものを有しており、イオン交換容量は、０．５〜１．０ｍｅｑ／ｍｌ湿潤樹脂）の範囲のもの。   (II) Strongly basic having macropores and micropores, macropores having a diameter of 2 to 20 μm, and micropores having a diameter of 30 to 300 nm (preferably a diameter of 42 to 240 nm) (provided that The pore diameter is in the range of 5.0 to 95.0% of the total pore volume), and the ion exchange capacity is in the range of 0.5 to 1.0 meq / ml wet resin) thing.

＜ＥＤＩ装置を用いた精製水の製造方法＞
ＥＤＩ装置の運転方法には特別なものはなく、通常の運転方法をそのまま適用できる。次に、ＥＤＩ装置の運転条件の好ましい例を挙げる。
供給水量：２５〜４５００Ｌ／hr
ＥＤＩ水量（脱塩水量）：２０〜４０００Ｌ／ｈｒ
濃縮水流量：供給液量の５％〜５０％の流量
印加電圧：３０〜１０００Ｖ
印加電流密度：０．１〜１．５Ａ／ｄｍ2 <Method for producing purified water using EDI device>
There is no special operation method for the EDI apparatus, and a normal operation method can be applied as it is. Next, the preferable example of the operating condition of an EDI apparatus is given.
Supply water volume: 25-4500L / hr
EDI water amount (desalted water amount): 20 to 4000 L / hr
Concentrated water flow rate: Flow rate of 5% to 50% of supply liquid Applied voltage: 30 to 1000V
Applied current density: 0.1 to 1.5 A / dm 2

なお、ＥＤＩ装置で処理する原水となる水道水や地下水は、必要に応じて、軟水装置、活性炭、ミクロフィルター等で前処理することもできる。   In addition, the tap water and groundwater used as the raw water processed with an EDI apparatus can also be pre-processed with a soft water apparatus, activated carbon, a micro filter, etc. as needed.

＜ＲＯ膜装置とＥＤＩ装置を組み合わせた２段階処理による精製水の製造方法＞
本発明の精製水の製造方法では、前記の前処理水を用いてＲＯ膜装置とＥＤＩ装置を組み合わせた２段階処理による精製水の製造方法も適用できる。ＲＯ膜処理との２段階処理により、ＥＤＩで除去対象となるイオン類の負荷を下げ、ＥＤＩの長寿命化とＥＤＩ処理水の高純度化が可能となる。 <Method for producing purified water by two-stage treatment combining RO membrane device and EDI device>
In the method for producing purified water according to the present invention, a method for producing purified water by a two-stage treatment in which the RO membrane device and the EDI device are combined using the pretreated water can also be applied. By the two-stage treatment with the RO membrane treatment, the load of ions to be removed by EDI can be reduced, and the life of EDI can be extended and the purity of EDI treated water can be increased.

１段目の処理では、ＲＯ膜装置を用いてＲＯ処理水を得る。
ＲＯ膜装置は、公知のものを用いることができ、例えば、ダイセン・メンブレン・システムズ株式会社より販売されている、ＳＶ０８−ＤＲＡ９８１、−ＤＲＡ９９１シリーズ、ＳＶ０４−ＤＲＡ９８１、−ＤＲＡ９９１シリーズ等を用いることができる。 In the first stage treatment, RO treated water is obtained using the RO membrane device.
As the RO membrane device, a known device can be used. For example, SV08-DRA981, -DRA991 series, SV04-DRA981, -DRA991 series and the like sold by Daisen Membrane Systems Co., Ltd. can be used. .

ＲＯ膜装置は、処理能力（処理水の製造能力）が３０〜５０００Ｌ／ｈｒのものを用いることができるが、前記範囲に限定されるものではなく、ＥＤＩ装置への供給量に応じて、適宜選択することができる。   As the RO membrane device, one having a treatment capacity (treatment water production capacity) of 30 to 5000 L / hr can be used, but is not limited to the above range, and is appropriately selected according to the supply amount to the EDI apparatus. You can choose.

次の２段目の処理では、上記した（I）又は（II）のＥＤＩ装置により、１段目の処理で得たＲＯ処理水を処理する。   In the next second stage treatment, the RO treated water obtained in the first stage treatment is treated by the EDI apparatus of (I) or (II) described above.

また、ＲＯ処理前の前処理水の水質によっては、ＲＯ膜装置処理を２段階として２段ＲＯ膜処理水をＥＤＩ装置に供給することもできる。   Further, depending on the quality of the pretreatment water before the RO treatment, the RO membrane device treatment can be performed in two stages and the two-stage RO membrane treatment water can be supplied to the EDI device.

更に、ＲＯ処理水中の炭酸イオンや硬度分の残存状況に応じて、ＲＯ処理水をＥＤＩ装置に供給する前に、脱気膜処理や軟水化処理を行っても良い。   Furthermore, a deaeration film treatment or a water softening treatment may be performed before supplying the RO treated water to the EDI device according to the remaining state of carbonate ions or hardness in the RO treated water.

なお、ＲＯ膜装置とＥＤＩ装置との間には、ＲＯ処理水を貯水するための貯水タンクを設け、貯水タンクの水をＥＤＩ装置に供給するようにしてもよい。
貯水タンクには、水位計、外部雰囲気からの雑菌等の混入を防ぐためのエアフィルター付きの通気孔を取り付けることができ、タンク内には、殺菌を目的として紫外線ランプを取り付けることもできる。 A water storage tank for storing the RO treated water may be provided between the RO membrane device and the EDI device, and the water in the water storage tank may be supplied to the EDI device.
The water storage tank can be provided with a water level gauge and a vent hole with an air filter for preventing contamination by germs from the outside atmosphere, and an ultraviolet lamp can be attached in the tank for the purpose of sterilization.

＜ＭＲ型の陰イオン交換樹脂を用いた精製水の製造方法＞
本発明の精製水の製造方法では、ＥＤＩ装置の脱塩室内に少なくとも1種以上のＭＲ型の強塩基性陰イオン交換樹脂を含む陰イオン交換樹脂を用いることにより、エンドトキシンや生菌の少ない精製水を得ることができる。 <Method for Producing Purified Water Using MR Type Anion Exchange Resin>
In the method for producing purified water according to the present invention, by using an anion exchange resin containing at least one MR type strongly basic anion exchange resin in the desalination chamber of the EDI apparatus, purification with less endotoxin and viable bacteria is achieved. You can get water.

ＥＤＩ装置の脱塩室内に充填される陽イオン交換樹脂との混床で用いられる陰イオン交換樹脂は、ＭＲ型の陰イオン交換樹脂単独でもよいし、２種以上のＭＲ型陰イオン交換樹脂を組合わせて使用することもできる。
また、ＭＲ型の陰イオン交換樹脂とゲル型の陰イオン交換樹脂を混合して充填することもできる。 The anion exchange resin used in the mixed bed with the cation exchange resin filled in the demineralization chamber of the EDI apparatus may be an MR type anion exchange resin alone, or two or more types of MR type anion exchange resins. It can also be used in combination.
Further, the MR type anion exchange resin and the gel type anion exchange resin may be mixed and filled.

前記のＭＲ型の陰イオン交換樹脂は、ミクロ孔が大きいものは、ゲル型の陰イオン交換樹脂よりも生菌やエンドトキシンの除去能に優れるが、イオン交換容量が小さくなる場合が多い。そのため、ミクロ孔が大きいＭＲ型陰イオン交換樹脂で、生菌とエンドトキシンを効率よく除去し、水中に含まれる無機イオン類はイオン交換容量の大きなゲル型の陰イオン交換樹脂で除去することにより、ＥＤＩ処理水中に残存する生菌とエンドトキシンを大きく減少させるとともに、比抵抗値の大きな超純水を得ることが可能となる。 The MR type anion exchange resin having a large micropore is superior to the gel type anion exchange resin in removing viable bacteria and endotoxin, but often has a small ion exchange capacity. Therefore, with MR type anion exchange resin with large micropores, viable bacteria and endotoxin are efficiently removed, and inorganic ions contained in water are removed with gel type anion exchange resin with a large ion exchange capacity, It is possible to greatly reduce viable bacteria and endotoxin remaining in the EDI-treated water and obtain ultrapure water having a large specific resistance value.

（１）ＥＤＩ装置
ＥＤＩ装置は、中央が脱塩室で、脱塩室の外方向両側が濃縮室、濃縮室の外方向両側が電極室から構成される５室系の装置（脱塩室の膜間距離は0.4cm，有効膜面積は297cm2）を用いた。
陽極側の脱塩室と濃縮室の間には陰イオン交換膜（陰イオン交換膜AHA；（株）アストム製）が配置され、濃縮室と電極室の間には陽イオン交換膜（陽イオン交換膜CMB；（株）アストム製）が配置されている。
陰極側の脱塩室と濃縮室の間には前記の陽イオン交換膜が配置され、濃縮室と電極室の間には前記の陰イオン交換膜が配置されている。濃縮室の膜間距離は二室とも0.4cmであり、電極室の電極とイオン交換膜との距離は両電極室とも0.4cmであった。また、濃縮室と電極間に配置されたイオン交換膜の有効膜面積は297cm2であった。
なお、陰イオン交換膜と陽イオン交換膜は、超純水約１０Ｌに約１５分間浸漬する浸漬洗浄を３回行ったものを用いた。
脱塩室には、下記の陰イオン交換樹脂と陽イオン交換樹脂が体積比１：１（60mlずつ）で充填されている。 (1) EDI device The EDI device is a five-chamber system consisting of a desalination chamber at the center, a concentrating chamber on both sides of the desalting chamber, and electrode chambers on both sides of the concentrating chamber. The distance between membranes was 0.4 cm and the effective membrane area was 297 cm 2 ).
An anion exchange membrane (anion exchange membrane AHA; manufactured by Astom Co., Ltd.) is disposed between the desalting chamber and the concentration chamber on the anode side, and a cation exchange membrane (cation) is disposed between the concentration chamber and the electrode chamber. Exchange membrane CMB (made by Astom Co., Ltd.) is arranged.
The cation exchange membrane is disposed between the desalting chamber and the concentration chamber on the cathode side, and the anion exchange membrane is disposed between the concentration chamber and the electrode chamber. The distance between the membranes in the concentrating chamber was 0.4 cm in both chambers, and the distance between the electrode in the electrode chamber and the ion exchange membrane was 0.4 cm in both electrode chambers. The effective membrane area of the ion exchange membrane disposed between the concentration chamber and the electrode was 297 cm 2 .
In addition, the anion exchange membrane and the cation exchange membrane used what performed immersion washing | cleaning 3 times immersed in about 10L of ultrapure water for about 15 minutes.
The desalting chamber is filled with the following anion exchange resin and cation exchange resin at a volume ratio of 1: 1 (each 60 ml).

（陰イオン交換樹脂）
表１に示す４種を用いた。アンバーライトIRA−900J（マクロ孔が直径２〜２０μm、ミクロ孔が直径２８〜４４ｎｍ）とアンバーライトIRA−904（マクロ孔が直径２〜２０μm、ミクロ孔が半径４２〜２４０ｎｍ）が実施例、アンバーライトIRA−400J、アンバーライトIRA−404Jが比較例の陰イオン交換樹脂となる。いずれの樹脂もオルガノ（株）製である。
（陽イオン交換樹脂）
アンバーライトIR−120B（強酸性，イオン交換容量：2.0meq/ml，オルガノ（株）製） (Anion exchange resin)
Four types shown in Table 1 were used. Amberlite IRA-900J (macropore diameter 2-20 μm, micropore diameter 28-44 nm) and Amberlite IRA-904 (macropore diameter 2-20 μm, micropore radius 42-240 nm) are examples, amber Light IRA-400J and Amberlite IRA-404J are comparative anion exchange resins. Both resins are manufactured by Organo Corporation.
(Cation exchange resin)
Amberlite IR-120B (strongly acidic, ion exchange capacity: 2.0 meq / ml, manufactured by Organo Corporation)

アンバーライトIRA−900JとアンバーライトIRA−904の細孔径は「イオン交換樹脂とその技術と応用（基礎編）」（改訂第２版1997年3月31日発行，編集発行者 オルガノ株式会社 IER部）のｐ37の「表1.9 MR形のイオン交換樹脂の細孔構造」に記載のものである。

Figure 0005658908
The pore size of Amberlite IRA-900J and Amberlite IRA-904 is “Ion-exchange resin and its technology and application (basic edition)” (Revised 2nd edition, published on March 31, 1997, Organizer IER Department) P37 of "Table 1.9 Pore structure of ion-exchange resin of MR type".
Figure 0005658908

（ＥＤＩの運転条件）
ＥＤＩ装置の脱塩室、濃縮室、電極室のそれぞれに対して、試料水を４１７ml/min、２００ml/min、１６７ml/minで通水しつつ、電流密度０．１１A/dm2で通電した。なお、前記流速条件は、前記ＥＤＩ装置を脱塩目的に使用する場合の実用通水速度である。 (EDI operating conditions)
The sample water was passed through the desalination chamber, concentration chamber, and electrode chamber of the EDI apparatus at 417 ml / min, 200 ml / min, and 167 ml / min while energizing at a current density of 0.11 A / dm 2 . The flow rate condition is a practical water flow rate when the EDI device is used for desalting purposes.

（２）測定方法
（2-1）試料水の調製方法
普通寒天培地にて毎月１回継代保存した緑膿菌（Pseudmonas aeruginosa GNB-139）を用いた。
普通ブイヨン１０ｍｌを分注したＬ字管にて３７℃で２０±２時間振とう培養後、さらに同培地（普通ブイヨン）３０ｍｌを分注した三角フラスコに移植し、３７℃で１８時間振とう培養した。
培養終了後、遠心集菌（４℃，6000r/m，11min）した菌体を滅菌生理食塩水で２回遠心洗浄した。
この洗浄菌体を滅菌生理食塩水３０ｍｌに再度懸濁し（菌濃度１０9CFC/ml）、その０．５ｍｌをＲＯ膜装置の処理水５０Ｌに添加し、菌濃度が１０3−１０4CFU/mlとなるように調整したものを試料水とした。なお、この試料水のＥＴ活性は１．５±０．６EU/mlであった。 (2) Measurement method (2-1) Sample water preparation method Pseudomonas aeruginosa GNB-139, which was stored once a month in a normal agar medium, was used.
After shaking culture for 20 ± 2 hours at 37 ° C in an L-shaped tube dispensed with 10 ml of normal broth, it was further transplanted to an Erlenmeyer flask dispensed with 30 ml of the same medium (normal broth) and cultured for 18 hours at 37 ° C. did.
After completion of the culture, the cells collected by centrifugation (4 ° C., 6000 r / m, 11 min) were washed twice by centrifugation with sterile physiological saline.
This washed cell is resuspended in 30 ml of sterile physiological saline (bacterial concentration 10 9 CFC / ml), 0.5 ml of this is added to 50 L of treated water in the RO membrane device, and the bacterial concentration is 10 3 -10 4 CFU / ml. The sample water was adjusted to be ml. The ET activity of this sample water was 1.5 ± 0.6 EU / ml.

（2-2）除菌効果の評価
除菌効果の評価は、次の方法で行った。
通電開始前を０分として、通電開始後５、１５、３０、６０、１２０、１８０分後に脱塩室流出水（ＥＤＩ処理水）を採水し、それぞれ滅菌生理食塩水で適当段階希釈したものを用い、Ｒ２Ａ寒天培地を用いた平板塗抹法により、２０〜２５℃で４〜７日間培養後の生菌数を測定した。
試料水（０分のもの）中の生菌数に対する各時間のＥＤＩ処理水中の生菌数の割合を算出し、生存率として評価した。１００％−生菌の生残率（％）が除菌率（％）を示すことになる。 (2-2) Evaluation of sterilization effect The sterilization effect was evaluated by the following method.
0 minutes before the start of energization, 5, 15, 30, 60, 120, 180 minutes after the start of energization, sampled desalination chamber effluent (EDI-treated water), and each diluted in appropriate stages with sterile physiological saline The viable cell count after culturing at 20 to 25 ° C. for 4 to 7 days was measured by a plate smearing method using an R2A agar medium.
The ratio of the number of viable bacteria in the EDI-treated water at each time to the number of viable bacteria in the sample water (0 minute) was calculated and evaluated as a survival rate. 100%-The survival rate (%) of viable bacteria indicates the eradication rate (%).

（2-3）ＥＴの除去効果の評価
上記の除菌効果の評価と同様にして採水したＥＤＩ処理水のＥＴ活性を、トキシノメーターミニ（和光純薬工業（株）製）を用いたリムルス（LAL）テスト比濁時間法により測定し、試料水（０分のもの）と各時間のＥＤＩ処理水のＥＴ活性を比較した。試料水（０分のもの）のＥＴ活性は、１．５±０．６EU/mlである。ＥＴ活性の低下が大きいものほど、ＥＴ除去効果が高いことを示す。 (2-3) Evaluation of ET removal effect Toxinometer mini (manufactured by Wako Pure Chemical Industries, Ltd.) was used for the ET activity of EDI-treated water collected in the same manner as the evaluation of the sterilization effect. Measured by the Limulus (LAL) test turbidimetric time method, the ET activity of the sample water (0 minute) and the EDI-treated water at each time was compared. The ET activity of sample water (0 min) is 1.5 ± 0.6 EU / ml. It shows that ET removal effect is so high that the fall of ET activity is large.

（2-4）イオン交換樹脂から脱離されたもの（イオン交換樹脂に吸着されていたもの）の細菌数の評価／ＥＴ活性の評価
運転終了後にＥＤＩ装置を解体し、脱塩室内のイオン交換樹脂を、液の流入口側（i）から流出口側（v）にかけて５区画（i〜v）に分け、各区画からイオン交換樹脂を約２０ｍｌずつ採取した。 (2-4) Evaluation of the number of bacteria / Et activity evaluation of those desorbed from the ion exchange resin (adsorbed on the ion exchange resin) After the operation was completed, the EDI device was disassembled and ion exchange in the desalination chamber The resin was divided into five compartments (i to v) from the liquid inlet side (i) to the outlet side (v), and about 20 ml of ion exchange resin was collected from each compartment.

次に、１ｍｏｌ／Ｌになるよう塩化ナトリウムを添加したリン酸緩衝液（ｐＨ8.0）２００ｍｌ中に、各区画から採取した約２０ｍｌのイオン交換樹脂を入れ、その後、約２０分間振とう撹拌して、イオン交換樹脂に吸着されている細菌及びＥＴをリン酸緩衝液（ｐＨ8.0）中に脱離させた。
このリン酸緩衝液を用いて、「（2-2）除菌効果の評価」及び「（2-3）ＥＴの除去効果の評価」と同様にして細菌数とＥＴ活性を測定した。
脱離したサンプル中の生菌数が多いほど、除菌効果が高いことを示し、脱離したサンプル中のＥＴ活性が高いほど、ＥＴ除去効果が高いことを示す。 Next, about 20 ml of ion exchange resin collected from each compartment is placed in 200 ml of phosphate buffer (pH 8.0) to which sodium chloride has been added so as to be 1 mol / L, and then shaken and stirred for about 20 minutes. Thus, bacteria and ET adsorbed on the ion exchange resin were desorbed in a phosphate buffer (pH 8.0).
Using this phosphate buffer, the number of bacteria and ET activity were measured in the same manner as in “(2-2) Evaluation of sterilization effect” and “(2-3) Evaluation of ET removal effect”.
The greater the number of viable bacteria in the detached sample, the higher the sterilization effect, and the higher the ET activity in the detached sample, the higher the ET removal effect.

（2-5）その他の評価
上記の除菌効果の評価と同様にして採水したＥＤＩ処理水の電気伝導度とｐＨを測定した。
電気伝導度は、電気伝導度計２００ＣＲ（Thorntonl社製）で測定し、ｐＨは、ｐＨメーター（堀場製作所製）にて測定した。 (2-5) Other evaluations The electrical conductivity and pH of EDI-treated water collected in the same manner as in the above evaluation of the sterilization effect were measured.
The electric conductivity was measured with an electric conductivity meter 200CR (manufactured by Thorntonl), and the pH was measured with a pH meter (manufactured by Horiba).

実施例１、比較例１
陰イオン交換樹脂として、表１に示す４種の陰イオン交換樹脂を充填したＥＤＩ装置を用いて、所定の運転条件にて試料水を処理した。処理水について「（2-2）除菌効果の評価（生菌の生残率（％）の変化）」を行った。結果を図１に示す。 Example 1 and Comparative Example 1
Using an EDI apparatus filled with four types of anion exchange resins shown in Table 1 as an anion exchange resin, sample water was treated under predetermined operating conditions. The treated water was subjected to “(2-2) Evaluation of sterilization effect (change in survival rate (%) of viable bacteria)”. The results are shown in FIG.

ＭＲ形の２つの陰イオン交換樹脂（実施例１）とゲル形の２つの陰イオン交換樹脂（比較例１）を用いた場合を比べると、ＭＲ形の２つの陰イオン交換樹脂の方が、除菌効果が高かった。
ＭＲ形の２つの陰イオン交換樹脂を比べると、イオン交換容量が小さい方（IRA−904）が、除菌効果が高かった。 Comparing the case where two MR type anion exchange resins (Example 1) and two gel type anion exchange resins (Comparative Example 1) were used, the two MR type anion exchange resins were The sterilization effect was high.
Comparing two MR type anion exchange resins, the smaller the ion exchange capacity (IRA-904), the higher the sterilization effect.

実施例２、比較例２
陰イオン交換樹脂として、表１に示す４種の陰イオン交換樹脂を充填したＥＤＩ装置を用いて、所定の運転条件にて試料水を処理した。処理水について「（2-3）ＥＴの除去効果の評価」を行った。結果を図２に示す。 Example 2 and Comparative Example 2
Using an EDI apparatus filled with four types of anion exchange resins shown in Table 1 as an anion exchange resin, sample water was treated under predetermined operating conditions. The treated water was subjected to “(2-3) Evaluation of ET removal effect”. The results are shown in FIG.

図２から明らかなとおり、IRA900J（MR形）、IRA904（MR形）（実施例２）、IRA400J（ゲル形）（比較例２）のＥＴ効果は同程度であった。なお、実用上の人工透析用水のＥＴ基準値は、０．０５EU／ｍｌである、   As is apparent from FIG. 2, the ET effects of IRA900J (MR type), IRA904 (MR type) (Example 2), and IRA400J (gel type) (Comparative Example 2) were comparable. In addition, the ET standard value of water for artificial dialysis practical use is 0.05 EU / ml.

実施例３、比較例３
陰イオン交換樹脂として、表１に示す４種の陰イオン交換樹脂を充填したＥＤＩ装置を用いて、所定の運転条件にて試料水を処理した。処理水について「（2-4）イオン交換樹脂から脱離されたものの生菌数の評価」を行った。結果を図３に示す。 Example 3 and Comparative Example 3
Using an EDI apparatus filled with four types of anion exchange resins shown in Table 1 as an anion exchange resin, sample water was treated under predetermined operating conditions. The treated water was subjected to “(2-4) Evaluation of the number of viable bacteria that were detached from the ion exchange resin”. The results are shown in FIG.

いずれの陰イオン交換樹脂の場合も、入り口側（i）側の脱離量（生菌数）が多く、流出口側（v）に向かうほど少なくなった。
ＭＲ形とゲル形では、ＭＲ形の陰イオン交換樹脂（実施例３）の方がより多くの生菌を吸着保持していた（除菌効果が高かった）。
IRA900J（MR形）とIRA904（MR形）では、IRA900J（MR形）の方がより多くの生菌を吸着保持していた（除菌効果が高かった）。 In any anion exchange resin, the amount of detachment (viable cell count) on the inlet side (i) side was large, and decreased toward the outlet side (v).
In the MR type and the gel type, the MR type anion exchange resin (Example 3) adsorbed and retained more viable bacteria (higher sterilization effect).
In IRA900J (MR type) and IRA904 (MR type), IRA900J (MR type) adsorbed and retained more viable bacteria (higher sterilization effect).

実施例４、比較例４
陰イオン交換樹脂として、表１に示す４種の陰イオン交換樹脂を充填したＥＤＩ装置を用いて、所定の運転条件にて試料水を処理した。処理水について「（2-4）イオン交換樹脂から脱離されたもののＥＴ活性の評価」を行った。結果を図４に示す。 Example 4 and Comparative Example 4
Using an EDI apparatus filled with four types of anion exchange resins shown in Table 1 as an anion exchange resin, sample water was treated under predetermined operating conditions. The treated water was subjected to “(2-4) Evaluation of ET activity of those desorbed from the ion exchange resin”. The results are shown in FIG.

いずれの陰イオン交換樹脂の場合も、入り口側（i）側の脱離サンプル中のＥＴ活性が高く、流出口側（v）に向かうほど小さくなった。
IRA900J（MR形）とIRA904（MR形）では、IRA900J（MR形）の脱離サンプル中の方が、ＥＴ活性が高かった（ＥＴ除去効果が高かった）。 In any of the anion exchange resins, the ET activity in the desorbed sample on the inlet side (i) side was high and became smaller toward the outlet side (v).
In IRA900J (MR type) and IRA904 (MR type), ET activity was higher in the desorbed sample of IRA900J (MR type) (ET removal effect was higher).

実施例５、比較例５
陰イオン交換樹脂として、表１に示す４種の陰イオン交換樹脂を充填したＥＤＩ装置を用いて、所定の運転条件にて試料水を処理した。処理水について「（2-5）その他の評価」により電気伝導度を測定した。結果を図５に示す。 Example 5, Comparative Example 5
Using an EDI apparatus filled with four types of anion exchange resins shown in Table 1 as an anion exchange resin, sample water was treated under predetermined operating conditions. The electrical conductivity of the treated water was measured by “(2-5) Other evaluations”. The results are shown in FIG.

実施例６、比較例６
陰イオン交換樹脂として、表１に示す４種の陰イオン交換樹脂を充填したＥＤＩ装置を用いて、所定の運転条件にて試料水を処理した。処理水について「（2-5）その他の評価」によりｐＨを測定した。結果を図６に示す。 Example 6 and Comparative Example 6
Using an EDI apparatus filled with four types of anion exchange resins shown in Table 1 as an anion exchange resin, sample water was treated under predetermined operating conditions. The pH of the treated water was measured by “(2-5) Other evaluations”. The results are shown in FIG.

参考例１〜４
参考例１（図７）は、ゲル形の陰イオン交換樹脂を使用し、ＥＤＩ装置を通電運転したときと、非通電で運転したときの生残率（％）の変化を測定した。
参考例２（図８）は、ＭＲ形の陰イオン交換樹脂を使用し、ＥＤＩ装置を通電運転したときと、非通電で運転したときの生残率（％）の変化を測定した。
参考例３（図９）は、ゲル形の陰イオン交換樹脂を使用し、ＥＤＩ装置を通電運転したときと、非通電で運転したときのＥＴ活性の変化を測定した。
参考例４（図１０）は、ＭＲ形の陰イオン交換樹脂を使用し、ＥＤＩ装置を通電運転したときと、非通電で運転したときのＥＴ活性の変化を測定した。 Reference Examples 1-4
In Reference Example 1 (FIG. 7), a gel-type anion exchange resin was used, and the change in the survival rate (%) when the EDI device was energized and deenergized was measured.
In Reference Example 2 (FIG. 8), an MR type anion exchange resin was used, and the change in the survival rate (%) was measured when the EDI device was operated with current and when it was not operated.
In Reference Example 3 (FIG. 9), a gel-type anion exchange resin was used, and the change in ET activity was measured when the EDI device was operated with current and when it was not operated.
In Reference Example 4 (FIG. 10), an anion exchange resin of MR type was used, and a change in ET activity was measured when the EDI apparatus was operated with current and when it was operated without current.

本発明の製造方法で得られる精製水は、人工透析用水や注射液等で使用する医療用の精製水、半導体の製造工程のような産業用の製造ラインにおいて使用する洗浄水等として適している。   The purified water obtained by the production method of the present invention is suitable as medical purified water used for artificial dialysis water, injection solution, etc., washing water used in industrial production lines such as semiconductor production processes, etc. .

Claims (5)

電気再生式脱イオン装置（ＥＤＩ装置）を用いた精製水の除菌およびエンドトキシンの除去方法であり、
前記ＥＤＩ装置が、イオン交換樹脂を備えたイオン交換室（脱塩室）、濃縮室、電極室（正及び負の電極室）を有するもので、印加電圧が３０〜１０００Ｖ、印加電流密度が０．１〜１．５Ａ／ｄｍ 2 で運転するものであり、
前記イオン交換室内に充填された陰イオン交換樹脂として少なくとも１種以上のＭＲ型の陰イオン交換樹脂を含む陰イオン交換樹脂を用いており、
前記ＭＲ型の陰イオン交換樹脂が、マクロ孔とミクロ孔を有する強塩基性のものであり、前記マクロ孔が直径２〜２０μmの範囲の孔であり、前記ミクロ孔が直径２０〜３００ｎｍの範囲の孔のものである、精製水の除菌およびエンドトキシンの除去方法。 A method for sterilizing purified water and removing endotoxin using an electric regeneration deionization device (EDI device),
The EDI apparatus has an ion exchange chamber (desalting chamber), an enrichment chamber, and electrode chambers (positive and negative electrode chambers) provided with an ion exchange resin . The applied voltage is 30 to 1000 V and the applied current density is 0. is intended to operate at .1~1.5A / dm 2,
An anion exchange resin containing at least one MR type anion exchange resin is used as the anion exchange resin filled in the ion exchange chamber,
The MR type anion exchange resin is strongly basic having macropores and micropores, the macropores are pores having a diameter of 2 to 20 μm, and the micropores are having a diameter of 20 to 300 nm. Of purified water and endotoxin , which are of the pores of 電気再生式脱イオン装置（ＥＤＩ装置）を用いた精製水の除菌およびエンドトキシンの除去方法であり、
前記ＥＤＩ装置が、イオン交換樹脂を備えたイオン交換室（脱塩室）、濃縮室、電極室（正及び負の電極室）を有するもので、印加電圧が３０〜１０００Ｖ、印加電流密度が０．１〜１．５Ａ／ｄｍ 2 で運転するものであり、
前記イオン交換室内に充填された陰イオン交換樹脂として少なくとも１種以上のＭＲ型の陰イオン交換樹脂を含む陰イオン交換樹脂を用いており、
前記ＭＲ型の陰イオン交換樹脂が、マクロ孔とミクロ孔を有する強塩基性のものであり、前記マクロ孔が直径２〜２０μmの範囲の孔で、前記ミクロ孔が直径２０〜６０ｎｍの範囲の孔であり、イオン交換容量が０．８〜１．５meq／ｍｌ（湿潤樹脂）のものである、精製水の除菌およびエンドトキシンの除去方法。 A method for sterilizing purified water and removing endotoxin using an electric regeneration deionization device (EDI device),
The EDI apparatus has an ion exchange chamber (desalting chamber), an enrichment chamber, and electrode chambers (positive and negative electrode chambers) provided with an ion exchange resin . The applied voltage is 30 to 1000 V and the applied current density is 0. is intended to run at .1~1.5A / dm 2,
An anion exchange resin containing at least one MR type anion exchange resin is used as the anion exchange resin filled in the ion exchange chamber,
The MR type anion exchange resin is strongly basic having macropores and micropores, the macropores are pores having a diameter of 2 to 20 μm, and the micropores are having a diameter of 20 to 60 nm. A method for disinfecting purified water and removing endotoxin, which is a pore and has an ion exchange capacity of 0.8 to 1.5 meq / ml (wet resin). 電気再生式脱イオン装置（ＥＤＩ装置）を用いた精製水の除菌およびエンドトキシンの除去方法であり、
前記ＥＤＩ装置が、イオン交換樹脂を備えたイオン交換室（脱塩室）、濃縮室、電極室（正及び負の電極室）を有するもので、印加電圧が３０〜１０００Ｖ、印加電流密度が０．１〜１．５Ａ／ｄｍ 2 で運転するものであり、
前記イオン交換室内に充填された陰イオン交換樹脂として少なくとも１種以上のＭＲ型の陰イオン交換樹脂を含む陰イオン交換樹脂を用いており、
前記ＭＲ型の陰イオン交換樹脂が、マクロ孔とミクロ孔を有する強塩基性のものであり、前記マクロ孔が直径２〜２０μmの範囲の孔で、前記ミクロ孔が直径３０〜３００ｎｍの範囲の孔であり、イオン交換容量が０．５〜１．０meq／ｍｌ（湿潤樹脂）のものである、精製水の除菌およびエンドトキシンの除去方法。 A method for sterilizing purified water and removing endotoxin using an electric regeneration deionization device (EDI device),
The EDI apparatus has an ion exchange chamber (desalting chamber), an enrichment chamber, and electrode chambers (positive and negative electrode chambers) provided with an ion exchange resin . The applied voltage is 30 to 1000 V and the applied current density is 0. is intended to operate at .1~1.5A / dm 2,
An anion exchange resin containing at least one MR type anion exchange resin is used as the anion exchange resin filled in the ion exchange chamber,
The MR type anion exchange resin is strongly basic having macropores and micropores, the macropores having a diameter in the range of 2 to 20 μm, and the micropores having a diameter in the range of 30 to 300 nm. A method for sterilizing purified water and removing endotoxin, which is a pore and has an ion exchange capacity of 0.5 to 1.0 meq / ml (wet resin). 逆浸透膜装置（ＲＯ膜装置）で処理した水をさらにＥＤＩ装置で処理する、請求項１〜３のいずれか１項に記載の精製水の除菌およびエンドトキシンの除去方法。 The method of disinfecting purified water and removing endotoxin according to any one of claims 1 to 3, wherein the water treated with a reverse osmosis membrane device (RO membrane device) is further treated with an EDI device. 精製水が人工透析用水である、請求項１〜４のいずれか１項記載の精製水の除菌およびエンドトキシンの除去方法。 The method for sterilizing purified water and removing endotoxin according to any one of claims 1 to 4, wherein the purified water is artificial dialysis water.
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