JP7698490B2 - How to prepare cation exchange resin - Google Patents
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本発明は、陽イオン交換樹脂をＨ形に変換するための調整方法に関し、イオン性不純物を含有する被処理水の精製方法に用いられる陽イオン交換樹脂を、再生又は前処理するための陽イオン交換樹脂の調整方法に関する。 The present invention relates to a method for adjusting a cation exchange resin to convert it to H-type, and to a method for adjusting a cation exchange resin for regenerating or pretreating a cation exchange resin used in a method for purifying water to be treated that contains ionic impurities.
半導体製造時におけるシリコンの洗浄工程等においては、各陽イオン不純物の濃度が１ｎｇ／Ｌ以下の超純水が求められている。水中のカルシウムやマグネシウムなどの硬度成分を主とする陽イオン不純物の濃度を低減する一次系での処理方法としては、弱酸性陽イオン交換樹脂を利用する方法が一般的である。 In the silicon washing process during semiconductor manufacturing, ultrapure water with a cationic impurity concentration of 1 ng/L or less is required. A common primary treatment method for reducing the concentration of cationic impurities in water, mainly hardness components such as calcium and magnesium, is to use a weakly acidic cation exchange resin.
例えば、引用文献１には、超純水製造の一次系処理として弱酸性陽イオン交換樹脂、強酸性陽イオン交換樹脂、弱塩基性陰イオン交換樹脂、強塩基性陰イオン交換樹脂を用いた超純水製造の一例が開示されている。 For example, cited reference 1 discloses an example of ultrapure water production using a weakly acidic cation exchange resin, a strongly acidic cation exchange resin, a weakly basic anion exchange resin, and a strongly basic anion exchange resin as the primary treatment for ultrapure water production.
弱酸性陽イオン交換樹脂を用いて、被処理水中の陽イオン不純物の除去を続けると、陽イオン不純物との結合によって、弱酸性陽イオン交換樹脂中の酸性のイオン交換基が使われてしまい、弱酸性陽イオン不純物を吸着できるイオン交換基の量が減少していく。 When weakly acidic cation exchange resin is used to continue removing cationic impurities from the water being treated, the acidic ion exchange groups in the weakly acidic cation exchange resin are used up by binding with the cationic impurities, and the amount of ion exchange groups available for adsorbing weakly acidic cationic impurities decreases.
そして、弱酸性陽イオン交換樹脂中のイオン交換基が全て使われてしまうと、弱酸性陽イオン不純物の除去性能が失われるので、その前に、一旦、被処理水の処理を中断して、弱酸性陽イオン交換樹脂を、塩酸、硫酸、硝酸等の酸水溶液に接触させて、Ｈ形に再生し、弱酸性陽イオン交換樹脂の吸着性を回復させる必要が生じる。 When all the ion exchange groups in the weakly acidic cation exchange resin are used up, it loses its ability to remove weakly acidic cation impurities, so before that happens, it is necessary to temporarily halt the treatment of the water being treated and bring the weakly acidic cation exchange resin into contact with an aqueous acid solution such as hydrochloric acid, sulfuric acid, or nitric acid to regenerate it into the H form and restore the adsorption properties of the weakly acidic cation exchange resin.
更に、弱酸性陽イオン交換樹脂に酸水溶液を接触させてＨ形に再生した後の弱酸性陽イオン交換樹脂には、酸水溶液由来のアニオン、例えば、酸水溶液として塩酸水溶液を用いた場合は、塩化物イオンが残留しているので、再生処理後のイオン交換樹脂を、超純水等で洗浄して、弱酸性陽イオン交換樹脂から酸水溶液由来のアニオンを除去し、アニオンの溶出を抑制する必要がある。 Furthermore, after the weakly acidic cation exchange resin is brought into contact with an aqueous acid solution and regenerated into the H form, the weakly acidic cation exchange resin still contains anions derived from the aqueous acid solution, for example, chloride ions when an aqueous hydrochloric acid solution is used as the aqueous acid solution. Therefore, it is necessary to wash the regenerated ion exchange resin with ultrapure water or the like to remove the anions derived from the aqueous acid solution from the weakly acidic cation exchange resin and suppress the elution of the anions.
例えば、引用文献２には、メーカー推奨の再生方式が記載されており、３～６質量％の塩酸又は０．５～０．８質量％の硫酸水溶液を、再生剤として用いることが記載されている。 For example, Cited Document 2 describes the regeneration method recommended by the manufacturer, which states that a 3-6% by mass aqueous solution of hydrochloric acid or a 0.5-0.8% by mass aqueous solution of sulfuric acid is used as the regenerant.
しかしながら、引用文献１の方法では、３～５％の酸性水溶液で弱酸性陽イオン交換樹脂を再生するため、また、引用文献２では、３～６質量％の塩酸又は０．５～０．８質量％の硫酸水溶液で弱酸性陽イオン交換樹脂を再生するため、イオン交換樹脂を再生した後の洗浄に、長時間を要してしまうという問題があった。そして、再生後の洗浄に時間を要することは、弱酸性陽イオン交換樹脂による超純水の精製プロセス全体の非効率化につながる。 However, in the method of cited document 1, the weakly acidic cation exchange resin is regenerated with a 3-5% acidic aqueous solution, and in cited document 2, the weakly acidic cation exchange resin is regenerated with a 3-6% by mass hydrochloric acid or 0.5-0.8% by mass sulfuric acid aqueous solution, so there is a problem that it takes a long time to wash the ion exchange resin after regeneration. Furthermore, the time required for washing after regeneration leads to inefficiency in the entire process of purifying ultrapure water using weakly acidic cation exchange resin.
従って、本発明は、Ｈ形弱酸性陽イオン交換樹脂の再生工程を行った後の洗浄の時間を低減することができる弱酸性陽イオン交換樹脂の調整方法を提供することにある。 Therefore, the present invention aims to provide a method for preparing a weakly acidic cation exchange resin that can reduce the washing time after performing a regeneration process for an H-type weakly acidic cation exchange resin.
このような技術背景のもと、本発明者らは、鋭意検討を重ねた結果、陽イオン交換樹脂の再生工程の際に、弱酸性陽イオン交換樹脂に接触させる酸水溶液の濃度を特定の範囲にすることにより、再生工程後の洗浄時間を短くすることができることを見出し、本発明を完成させるに至った。 In light of this technical background, the inventors conducted extensive research and discovered that by setting the concentration of the aqueous acid solution that is brought into contact with the weakly acidic cation exchange resin during the cation exchange resin regeneration process within a specific range, it is possible to shorten the washing time after the regeneration process, which led to the completion of the present invention.
すなわち、本発明（１）は、陽イオン交換樹脂に酸水溶液を接触させることにより、該陽イオン交換樹脂をＨ形に変換する再生工程と、
Ｈ形に変換されたＨ形陽イオン交換樹脂に洗浄水を接触させることにより、該Ｈ形陽イオン交換樹脂を洗浄する洗浄工程と、
を有すること、
該陽イオン交換樹脂は、弱酸性陽イオン交換樹脂であり、
該酸水溶液の規定度が、０．１０～０．５０Ｎであること、
該酸水溶液を、ＳＶ８～４０ｈ
-1
の通液速度で通液することにより、該再生工程を行うこと、
該再生工程における、該酸水溶液の規定度Ａと、該酸水溶液の通液速度Ｂの関係が、下記式（１）：
Ａ×Ｂ≦４．５（１）
（式中、Ａは、酸水溶液の規定度（Ｎ）であり、Ｂは、酸水溶液の通液速度ＳＶ（ｈ
-1
）である。）
を満たすこと、
を特徴とする陽イオン交換樹脂の調整方法を提供するものである。
That is, the present invention (1) provides a method for producing a cation exchange resin by converting the cation exchange resin into an H-type cation exchange resin, comprising:
a washing step of washing the H-form cation exchange resin by contacting the H-form cation exchange resin converted to the H-form with wash water;
having
The cation exchange resin is a weakly acidic cation exchange resin,
The normality of the aqueous acid solution is 0.10 to 0.50N;
The regeneration step is carried out by passing the aqueous acid solution through the column at a flow rate of SV8 to 40 h -1.
In the regeneration step, the relationship between the normality A of the aqueous acid solution and the flow rate B of the aqueous acid solution is expressed by the following formula (1):
A × B ≦ 4.5 (1)
(In the formula, A is the normality (N) of the acid aqueous solution, and B is the flow rate SV (h −1 ) of the acid aqueous solution.)
To satisfy the following:
The present invention provides a method for preparing a cation exchange resin, comprising the steps of:
また、本発明（２）は、前記陽イオン交換樹脂が、イオン交換基として、カルボキシル基を有することを特徴とする（１）の陽イオン交換樹脂の調整方法を提供するものである。 The present invention ( 2 ) also provides a method for preparing a cation exchange resin according to ( 1 ), wherein the cation exchange resin has a carboxyl group as an ion exchange group.
また、本発明（３）は、前記陽イオン交換樹脂の基体が、アクリル酸又はメタクリル酸－ジビニルベンゼン系共重合体であることを特徴とする（１）又は（２）の陽イオン交換樹脂の調整方法を提供するものである。
The present invention ( 3 ) also provides a method for preparing a cation exchange resin according to (1) or (2) , characterized in that the base of the cation exchange resin is an acrylic acid or methacrylic acid-divinylbenzene copolymer.
本発明によれば、Ｈ形弱酸性陽イオン交換樹脂の再生工程を行った後の洗浄の時間を低減することができる弱酸性陽イオン交換樹脂の調整方法を提供することができる。 According to the present invention, a method for preparing a weakly acidic cation exchange resin can be provided that can reduce the cleaning time after performing a regeneration process for an H-type weakly acidic cation exchange resin.
本発明の陽イオン交換樹脂の調整方法は、陽イオン交換樹脂に酸水溶液を接触させることにより、該陽イオン交換樹脂をＨ形に変換する再生工程と、
Ｈ形に変換されたＨ形陽イオン交換樹脂に洗浄水を接触させることにより、該Ｈ形陽イオン交換樹脂を洗浄する洗浄工程と、
を有すること、
該陽イオン交換樹脂は、弱酸性陽イオン交換樹脂であり、
該酸水溶液の規定度が、０．１０～０．５０Ｎであること、
を特徴とする陽イオン交換樹脂の調整方法である。
The method for preparing a cation exchange resin of the present invention includes a regeneration step of converting the cation exchange resin into an H-form cation exchange resin by contacting the cation exchange resin with an aqueous acid solution;
a washing step of washing the H-form cation exchange resin by contacting the H-form cation exchange resin converted to the H-form with wash water;
having
The cation exchange resin is a weakly acidic cation exchange resin,
The normality of the aqueous acid solution is 0.10 to 0.50N;
The present invention relates to a method for preparing a cation exchange resin.
本発明の陽イオン交換樹脂の調整方法は、再生工程と、洗浄工程と、を有する。 The method for preparing a cation exchange resin of the present invention includes a regeneration process and a washing process.
再生工程は、陽イオン交換樹脂に、酸水溶液を接触させることにより、陽イオン交換樹脂をＨ形に変換する工程である。 The regeneration process involves converting the cation exchange resin to H-form by contacting it with an aqueous acid solution.
再生工程において、酸水溶液に接触させる陽イオン交換樹脂は、弱酸性陽イオン交換樹脂である。弱酸性陽イオン交換樹脂は、自身が持つカルボキシル基、チオール基、フェノール基、アルコール基等の弱酸性の官能基の乖離度が低いため、強酸性陽イオン交換樹脂に比べ、カルシウム、マグネシウム等の硬度成分を主とした吸着イオンに対する酸による再生効率に優れる。 In the regeneration process, the cation exchange resin that is brought into contact with the acidic aqueous solution is a weakly acidic cation exchange resin. Weakly acidic cation exchange resins have a low degree of dissociation of their own weakly acidic functional groups, such as carboxyl groups, thiol groups, phenol groups, and alcohol groups, and therefore have superior regeneration efficiency with acid for adsorbed ions, mainly hardness components such as calcium and magnesium, compared to strongly acidic cation exchange resins.
弱酸性陽イオン交換樹脂に係る陽イオン交換基としては、特に制限されず、カルボキシル基、チオール基、フェノール基、アルコール基等が挙げられる。これらのうち、陽イオン交換基としては、カルボキシル基が好ましい。 The cation exchange group of the weakly acidic cation exchange resin is not particularly limited, and examples thereof include a carboxyl group, a thiol group, a phenol group, and an alcohol group. Of these, the cation exchange group is preferably a carboxyl group.
弱酸性陽イオン交換樹脂は、樹脂製の基体に陽イオン交換基が導入されたイオン交換樹脂であれば、特に制限されず、粉末状、ビーズ状、膜状など種々の形態のものであってもよく、また、ゲル型イオン交換樹脂又は多孔性型イオン交換樹脂のいずれであってもよい。 The weakly acidic cation exchange resin is not particularly limited as long as it is an ion exchange resin in which cation exchange groups have been introduced into a resin base, and may be in various forms such as powder, beads, or membrane, and may be either a gel-type ion exchange resin or a porous ion exchange resin.
ゲル型イオン交換樹脂及び多孔性型イオン交換樹脂は、イオン交換樹脂のミクロ構造に基づく分類である。このうちゲル型イオン交換樹脂とは、スチレンとジビニルベンゼンを無溶媒で重合させたものを基体とするイオン交換樹脂で不均一に架橋したゲル状の構造を有し、最も古典的なイオン交換樹脂を意味する。また、多孔性型イオン交換樹脂は、重合の際に溶媒を使用することによって孔径２０ｎｍから１００ｎｍ程度のマクロポアが形成された樹脂を基体とするイオン交換樹脂を意味し、ＭＰ型（マクロポーラス型）、ＭＲ型（マクロレティキュラー型）と呼ばれているものも含む。多孔性型イオン交換樹脂は、マクロポアが連続しておらず均一度にも欠けるためゲル型樹脂に比べてイオン交換容量は低いが、物理的強度は高く浸透圧や機械的圧力に対する耐性に優れている。 Gel-type ion exchange resins and porous-type ion exchange resins are classified based on the microstructure of ion exchange resins. Among these, gel-type ion exchange resins are ion exchange resins based on the polymerized styrene and divinylbenzene without a solvent, and have a non-uniformly cross-linked gel-like structure, which is the most classic ion exchange resin. In addition, porous-type ion exchange resins are ion exchange resins based on resins in which macropores with pore sizes of about 20 nm to 100 nm are formed by using a solvent during polymerization, and include those called MP type (macroporous type) and MR type (macroreticular type). Porous-type ion exchange resins have macropores that are not continuous and lack uniformity, so they have a lower ion exchange capacity than gel-type resins, but they have high physical strength and excellent resistance to osmotic pressure and mechanical pressure.
陽イオン交換基が結合する基体としては、例えば、架橋ポリスチレン、スチレン－ジビニルベンゼン共重合体等のスチレン系化合物や、フェノール類、アルデヒド類の縮合体や、アクリル酸又はメタクリル酸－ジビニルベンゼン共重合体等の架橋ポリアクリル酸等から選ばれる１種以上が好ましく、架橋ポリアクリル酸がより好ましく、アクリル酸又はメタクリル酸－ジビニルベンゼン共重合体が特に好ましい。 The substrate to which the cation exchange group is bonded is preferably one or more selected from, for example, styrene-based compounds such as cross-linked polystyrene and styrene-divinylbenzene copolymer, condensates of phenols and aldehydes, and cross-linked polyacrylic acids such as acrylic acid or methacrylic acid-divinylbenzene copolymer, more preferably cross-linked polyacrylic acid, and particularly preferably acrylic acid or methacrylic acid-divinylbenzene copolymer.
弱酸性陽イオン交換樹脂としては、弱酸性官能基を有し、アクリル酸又はメタクリル酸－ジビニルベンゼン共重合体を基体とするＭＲ型の弱酸性陽イオン交換樹脂が好ましい。 As the weakly acidic cation exchange resin, a MR type weakly acidic cation exchange resin having a weakly acidic functional group and based on an acrylic acid or methacrylic acid-divinylbenzene copolymer is preferred.
弱酸性陽イオン交換樹脂の形状は、特に制限されないが、例えば粒形状を有する場合、その平均粒径は、好ましくは０．２～１．０ｍｍ、より好ましくは０．４～０．８ｍｍである。 The shape of the weakly acidic cation exchange resin is not particularly limited, but for example, if it has a granular shape, the average particle size is preferably 0.2 to 1.0 mm, more preferably 0.4 to 0.8 mm.
弱酸性陽イオン交換樹脂としては、市販品であってもあってもよく、このような弱酸性陽イオン交換樹脂としては、ＤｕＰｏｎｔ社製 ＡＭＢＥＲＬＩＴＥ ＨＰＲ８４００、ＡＭＢＥＲＬＩＴＥ ＩＲＣ７６、ＡＭＢＥＲＬＩＴＥ ＩＲＣ８６、三菱ケミカル社製 ＤＩＡＩＯＮ ＷＫ６０Ｌ等が挙げられる。 The weakly acidic cation exchange resin may be a commercially available product. Examples of such a weakly acidic cation exchange resin include AMBERLITE HPR8400, AMBERLITE IRC76, and AMBERLITE IRC86 manufactured by DuPont, and DIAION WK60L manufactured by Mitsubishi Chemical Corporation.
再生工程において、酸水溶液に接触させる弱酸性陽イオン交換樹脂としては、被処理水の精製に用いたことによって、再生が必要となった弱酸性陽イオン交換樹脂、すなわち、陽イオン交換基に陽イオン不純物が吸着している弱酸性陽イオン交換樹脂が挙げられる。 In the regeneration process, the weakly acidic cation exchange resin that is brought into contact with the acid aqueous solution is, for example, a weakly acidic cation exchange resin that has been used to purify the water to be treated and thus needs to be regenerated, i.e., a weakly acidic cation exchange resin in which cationic impurities are adsorbed to the cation exchange groups.
再生工程において、弱酸性陽イオン交換樹脂に接触させる酸水溶液は、塩酸、硫酸、硝酸等の酸の水溶液である。 In the regeneration process, the aqueous acid solution that is brought into contact with the weakly acidic cation exchange resin is an aqueous solution of an acid such as hydrochloric acid, sulfuric acid, or nitric acid.
酸水溶液の規定度は、０．１０～０．５０Ｎ（当量／Ｌ）、好ましくは０．１０～０．２０Ｎである。酸水溶液の規定度が上記範囲にあることにより、洗浄工程の洗浄時間を短くすることができる。一方、酸水溶液の規定度が、上記範囲未満だと、弱酸性陽イオン交換樹脂のＨ形への変換が不十分となり、また、上記範囲を超えると、洗浄工程での洗浄時間が長くなる。 The normality of the aqueous acid solution is 0.10 to 0.50 N (equivalents/L), preferably 0.10 to 0.20 N. By having the normality of the aqueous acid solution in the above range, the washing time in the washing step can be shortened. On the other hand, if the normality of the aqueous acid solution is less than the above range, the conversion of the weakly acidic cation exchange resin to the H form will be insufficient, and if it exceeds the above range, the washing time in the washing step will be longer.
再生工程において、弱酸性陽イオン交換樹脂に接触させる酸水溶液の温度は、特に制限されず、酸水溶液の種類、イオン交換樹脂の耐熱温度等に応じて、適宜選択される。 In the regeneration process, the temperature of the aqueous acid solution brought into contact with the weakly acidic cation exchange resin is not particularly limited and is appropriately selected depending on the type of aqueous acid solution, the heat resistance temperature of the ion exchange resin, etc.
再生工程において、弱酸性陽イオン交換樹脂に酸水溶液を接触させる方法としては、弱酸性陽イオン交換樹脂を陽イオン交換樹脂充填容器に充填して、陽イオン交換樹脂充填容器内に、陽イオン交換樹脂の樹脂床を形成させ、次いで、陽イオン交換樹脂床が充填されている陽イオン交換樹脂充填容器に、酸水溶液を通液し、陽イオン交換樹脂充填容器内の陽イオン交換樹脂に酸水溶液を接触させ、陽イオン交換樹脂に接触させた後の酸水溶液を陽イオン交換樹脂充填容器から排出する方法が挙げられる。 In the regeneration process, the method of contacting the weakly acidic cation exchange resin with the acid aqueous solution includes filling a container filled with the weakly acidic cation exchange resin to form a resin bed of the cation exchange resin in the container filled with the cation exchange resin, then passing the acid aqueous solution through the container filled with the cation exchange resin bed to bring the acid aqueous solution into contact with the cation exchange resin in the container filled with the cation exchange resin, and discharging the acid aqueous solution after contact with the cation exchange resin from the container filled with the cation exchange resin.
他には、再生工程において、弱酸性陽イオン交換樹脂に酸水溶液を接触させる方法としては、弱酸性陽イオン交換樹脂を陽イオン交換樹脂充填容器に充填し、陽イオン交換樹脂床が充填されている陽イオン交換樹脂充填容器に、酸水溶液を導入して浸漬し、陽イオン交換樹脂充填容器内の陽イオン交換樹脂に酸水溶液を接触させ、陽イオン交換樹脂に接触させた後の酸水溶液を陽イオン交換樹脂充填容器から排出する等の方法が挙げられる。 Other methods for contacting the weakly acidic cation exchange resin with the acidic aqueous solution in the regeneration process include filling a container filled with the weakly acidic cation exchange resin, introducing an acidic aqueous solution into the container filled with the cation exchange resin bed, soaking the container in the cation exchange resin bed, contacting the acidic aqueous solution with the cation exchange resin in the container, and discharging the acidic aqueous solution after contacting the cation exchange resin from the container.
陽イオン交換樹脂充填容器内に充填されている弱酸性陽イオン交換樹脂床に、酸水溶液を通液することにより、弱酸性陽イオン交換樹脂に酸水溶液を接触させる場合、陽イオン交換樹脂床への酸水溶液の通液速度ＳＶは、好ましくは８～４０ｈ－１である。 When the acid aqueous solution is brought into contact with the weakly acidic cation exchange resin by passing the acid aqueous solution through a weakly acidic cation exchange resin bed packed in a cation exchange resin-packed container, the passing velocity SV of the acid aqueous solution through the cation exchange resin bed is preferably 8 to 40 h -1 .
そして、再生工程において、酸水溶液の規定度が０．１０～０．５０Ｎ、好ましくは０．１０～０．２０Ｎであり、且つ、陽イオン交換樹脂床への酸水溶液の通液速度ＳＶが８～４０ｈ－１であることが、再生工程の時間を延長することなく、洗浄後に比抵抗を所定の値まで、短く到達させることができる点で好ましい。 In the regeneration step, it is preferable that the normality of the aqueous acid solution is 0.10 to 0.50 N, preferably 0.10 to 0.20 N, and that the flow rate SV of the aqueous acid solution through the cation exchange resin bed is 8 to 40 h −1 , since this allows the resistivity to reach a predetermined value after cleaning in a short time without extending the time of the regeneration step.
陽イオン交換樹脂充填容器内に充填されている弱酸性陽イオン交換樹脂床に、酸水溶液を通液することにより、弱酸性陽イオン交換樹脂に酸水溶液を接触させる場合、酸水溶液の規定度Ａと、陽イオン交換樹脂床への酸水溶液の通液速度Ｂとの関係が、下記式（１）：
Ａ×Ｂ≦４．５ （１）
（式中、Ａは、酸水溶液の規定度（Ｎ）であり、Ｂは、酸水溶液の通液速度ＳＶ（ｈ－１）である。）
を満たすことが好ましい。酸水溶液の規定度Ａと、陽イオン交換樹脂床への酸水溶液の通液速度Ｂとの関係が、上記一般式（１）を満たすことにより、再生工程の時間を短くすることができる。より好ましい範囲としては、０．０１≦Ａ×Ｂ≦４．５であり、特に好ましい範囲としては０．１≦Ａ×Ｂ≦４．０である。Ａ×Ｂの値が０．０１より小さくなると、再生に必要な酸の総量と酸水溶液の規定度Ａの範囲０．１０～０．５０に対して、通水ＳＶが１以下となるため、再生工程の時間が非常に長くなる。一方、Ａ×Ｂの値が４．５を超えると、ＳＶが高くなるため、つまりは通水流速が速くなるため、再生に必要な酸水溶液とイオン交換樹脂の接触時間低下による再生不良が起こり易くなる。
When the acid aqueous solution is brought into contact with the weakly acidic cation exchange resin by passing the acid aqueous solution through a weakly acidic cation exchange resin bed packed in a cation exchange resin-packed container, the relationship between the normality A of the acid aqueous solution and the passing rate B of the acid aqueous solution through the cation exchange resin bed is expressed by the following formula (1):
A × B≦4.5 (1)
(In the formula, A is the normality (N) of the aqueous acid solution, and B is the flow rate SV (h −1 ) of the aqueous acid solution.)
It is preferable to satisfy the above. The relationship between the normality A of the acid aqueous solution and the flow rate B of the acid aqueous solution to the cation exchange resin bed satisfies the above general formula (1), so that the time of the regeneration step can be shortened. A more preferable range is 0.01≦A×B≦4.5, and a particularly preferable range is 0.1≦A×B≦4.0. When the value of A×B is smaller than 0.01, the water flow SV is 1 or less for the total amount of acid required for regeneration and the normality A of the acid aqueous solution in the range of 0.10 to 0.50, so that the time of the regeneration step becomes very long. On the other hand, when the value of A×B exceeds 4.5, the SV becomes high, that is, the water flow rate becomes fast, so that regeneration failure due to the decrease in the contact time between the acid aqueous solution required for regeneration and the ion exchange resin is likely to occur.
そして、再生工程を行うことにより、陽イオン交換樹脂の陽イオン交換基から、陽イオン不純物が脱離し、陽イオン交換樹脂から陽イオン不純物が除去されて、陽イオン交換樹脂の陽イオン交換基は、Ｈ形に変換されるので、陽イオン交換樹脂がＨ形陽イオン交換樹脂に変換されて、陽イオン交換樹脂が再生される。 Then, by carrying out the regeneration process, cationic impurities are released from the cation exchange groups of the cation exchange resin, the cationic impurities are removed from the cation exchange resin, and the cation exchange groups of the cation exchange resin are converted to H-form, so that the cation exchange resin is converted to H-form cation exchange resin, and the cation exchange resin is regenerated.
洗浄工程は、再生工程を行いＨ形に変換された弱酸性陽イオン交換樹脂（以下、Ｈ形陽イオン交換樹脂とも記載する。）に、洗浄水を接触させることにより、Ｈ形陽イオン交換樹脂を洗浄する工程である。再生工程を行った後のＨ形陽イオン交換樹脂の内部及び表面並びに陽イオン交換樹脂の粒子間の隙間には、酸水溶液由来のアニオンが残存しているので、Ｈ形陽イオン交換樹脂を用いて被処理水の精製を行う前に、Ｈ形陽イオン交換樹脂に残存している酸水溶液由来のアニオンを除去する必要がある。そこで、洗浄工程を行うことにより、Ｈ形陽イオン交換樹脂の内部及び表面並びに陽イオン交換樹脂の粒子間の隙間に残存している酸水溶液由来のアニオンを除去する。 The washing process is a process for washing the H-type cation exchange resin by contacting the weakly acidic cation exchange resin (hereinafter also referred to as H-type cation exchange resin) that has been converted to H-type by the regeneration process with washing water. After the regeneration process, anions derived from the acid aqueous solution remain inside and on the surface of the H-type cation exchange resin and in the gaps between the particles of the cation exchange resin. Therefore, before purifying the water to be treated using the H-type cation exchange resin, it is necessary to remove the anions derived from the acid aqueous solution remaining in the H-type cation exchange resin. Therefore, by carrying out the washing process, the anions derived from the acid aqueous solution remaining inside and on the surface of the H-type cation exchange resin and in the gaps between the particles of the cation exchange resin are removed.
洗浄工程において、Ｈ形弱酸性陽イオン交換樹脂に接触させる洗浄水は、不純物含有量が少ないほど好ましく、洗浄水中の金属含有量が少ないほど望ましい。 In the washing process, the washing water that is brought into contact with the H-type weakly acidic cation exchange resin preferably has a lower impurity content, and the lower the metal content in the washing water, the more desirable it is.
洗浄工程において、Ｈ形陽イオン交換樹脂に接触させる洗浄水の温度は、特に制限されず、イオン交換樹脂の耐熱温度等に応じて、適宜選択される。 In the washing process, the temperature of the washing water that is brought into contact with the H-type cation exchange resin is not particularly limited and is appropriately selected depending on the heat resistance temperature of the ion exchange resin, etc.
洗浄工程において、Ｈ形陽イオン交換樹脂に洗浄水を接触させる方法としては、Ｈ形陽イオン交換樹脂が充填されている陽イオン交換樹脂充填容器に、洗浄水を通液し、陽イオン交換樹脂充填容器内のＨ形陽イオン交換樹脂に洗浄水を接触させ、Ｈ形陽イオン交換樹脂に接触させた後の洗浄水を陽イオン交換樹脂充填容器から排出する方法が挙げられる。 In the washing step, the method of bringing the washing water into contact with the H-type cation exchange resin includes passing the washing water through a container filled with H-type cation exchange resin, bringing the washing water into contact with the H-type cation exchange resin in the container, and discharging the washing water from the container after contacting with the H-type cation exchange resin.
他には、洗浄工程において、Ｈ形陽イオン交換樹脂に洗浄水を接触させる方法としては、Ｈ形陽イオン交換樹脂を陽イオン交換樹脂充填容器に充填し、Ｈ形陽イオン交換樹脂床が充填されている陽イオン交換樹脂充填容器に、洗浄水を導入して浸漬し、陽イオン交換樹脂充填容器内のＨ形陽イオン交換樹脂に洗浄水を接触させ、Ｈ形陽イオン交換樹脂に接触させた後の洗浄水を陽イオン交換樹脂充填容器から排出する方法等が挙げられる。 Another method for contacting the H-type cation exchange resin with washing water in the washing step includes filling a cation exchange resin-filled container with H-type cation exchange resin, introducing washing water into the cation exchange resin-filled container filled with the H-type cation exchange resin bed and immersing the container in washing water, contacting the washing water with the H-type cation exchange resin in the cation exchange resin-filled container, and discharging the washing water from the cation exchange resin-filled container after contacting the H-type cation exchange resin.
陽イオン交換樹脂充填容器内に充填されているＨ形陽イオン交換樹脂床に、洗浄水を通液することにより、Ｈ形陽イオン交換樹脂に洗浄水を接触させる場合、Ｈ形陽イオン交換樹脂床への洗浄水の通液速度ＳＶは、好ましくは１～１００ｈ－１である。 When the washing water is passed through an H-type cation exchange resin bed packed in a cation exchange resin-packed container to contact the H-type cation exchange resin, the passing velocity SV of the washing water through the H-type cation exchange resin bed is preferably 1 to 100 h −1 .
そして、洗浄工程を行うことにより、陽イオン交換樹脂は、被処理水の精製に用いられるＨ形陽イオン交換樹脂に調整される。 Then, by carrying out a cleaning process, the cation exchange resin is adjusted to H-type cation exchange resin, which is used to purify the treated water.
本発明の陽イオン交換樹脂の調整方法を行った後は、再生工程及び洗浄工程が施されたＨ形陽イオン交換樹脂を用いて、被処理水を精製する精製工程を行い、処理水を得る。 After carrying out the cation exchange resin preparation method of the present invention, a purification process is carried out to purify the water to be treated using the H-type cation exchange resin that has been subjected to the regeneration process and washing process, thereby obtaining treated water.
精製工程において、被処理水の温度、Ｈ形陽イオン交換樹脂への通液速度、通水時間、Ｈ形陽イオン交換樹脂の樹脂量、樹脂層高等の精製処理条件は、被処理水の水質を踏まえて適宜選択される。 In the purification process, purification processing conditions such as the temperature of the water to be treated, the flow rate through the H-type cation exchange resin, the water flow time, the amount of H-type cation exchange resin, and the resin layer height are appropriately selected based on the water quality of the water to be treated.
弱酸性陽イオン交換樹脂の処理水中の硬度成分を主とする陽イオン不純物の含有量であるが、各陽イオン不純物の含有量が、好ましくは１００μｇ／Ｌ以下、特に好ましくは１０μｇ／Ｌ以下である。弱酸性陽イオン交換樹脂の処理水は、強酸性陽イオン交換樹脂や塩基性陰イオン交換樹脂、あるいは逆浸透（ＲＯ）膜や電気式脱塩装置などの処理を経て、イオン性不純物の濃度が極めて低いことが求められる半導体製造用の超純水として好適に用いられる。 The content of cationic impurities, mainly hardness components, in the water treated with the weakly acidic cation exchange resin is preferably 100 μg/L or less, and particularly preferably 10 μg/L or less. The water treated with the weakly acidic cation exchange resin is preferably used as ultrapure water for semiconductor manufacturing, which requires an extremely low concentration of ionic impurities, after being processed with a strongly acidic cation exchange resin, a basic anion exchange resin, a reverse osmosis (RO) membrane, an electrical demineralization device, or the like.
そして、精製工程では、Ｈ形陽イオン交換樹脂の陽イオン交換基に被処理水中の陽イオン不純物が吸着するので、精製を続けると、Ｈ形陽イオン交換樹脂中の陽イオン不純物を吸着できる陽イオン交換基の量が減少していく。そのため、Ｈ形陽イオン交換樹脂中の陽イオン不純物を吸着できる陽イオン交換基の全てが、陽イオン不純物の吸着に使用されて、陽イオン不純物除去性能が消失する前に、精製工程を中断して、再び、本発明の陽イオン交換樹脂の調整方法を行う。 In the purification process, cationic impurities in the water being treated are adsorbed to the cation exchange groups of the H-type cation exchange resin, so as purification continues, the amount of cation exchange groups in the H-type cation exchange resin that can adsorb cationic impurities decreases. Therefore, before all of the cation exchange groups in the H-type cation exchange resin that can adsorb cationic impurities are used to adsorb the cationic impurities and the cationic impurity removal performance is lost, the purification process is interrupted and the cation exchange resin adjustment method of the present invention is carried out again.
本発明の陽イオン交換樹脂の調整方法では、再生工程を行った後の洗浄工程において、Ｈ形陽イオン交換樹脂に残存している酸水溶液由来のアニオンの量を、速やかに減少させることができるので、洗浄時間を短くすることができる。例えば、本発明の陽イオン交換樹脂の調整方法では、再生工程を行った後の洗浄工程において、陽イオン交換樹脂に接触させた後の洗浄水の比抵抗値が１０ＭΩ・ｃｍに達するまでの時間が短くなる。また、例えば、本発明の陽イオン交換樹脂の調整方法では、再生工程を行った後の洗浄工程において、洗浄開始から１時間後の陽イオン交換樹脂に接触させた後の洗浄水の比抵抗値が、従来の陽イオン交換樹脂の再生方法に比べ高くなる。 In the method for preparing a cation exchange resin of the present invention, the amount of anions derived from the acid aqueous solution remaining in the H-type cation exchange resin can be quickly reduced in the washing step after the regeneration step, and therefore the washing time can be shortened. For example, in the method for preparing a cation exchange resin of the present invention, in the washing step after the regeneration step, the time until the resistivity value of the washing water after contacting with the cation exchange resin reaches 10 MΩ·cm is shortened. Also, for example, in the method for preparing a cation exchange resin of the present invention, in the washing step after the regeneration step, the resistivity value of the washing water after contacting with the cation exchange resin one hour after the start of washing is higher than that of the conventional method for regenerating a cation exchange resin.
以下では、実施例を示して本発明を更に詳細に説明するが、本発明はそれに限定されるものではない。 The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.
（実施例１）
弱酸性陽イオン交換樹脂（ＡＭＢＥＲＬＩＴＥ ＨＰＲ８４００－ＨＧ、オルガノ社製）を、樹脂量として５００ｍＬ（５００ｍＬ－Ｒ）充填したカラムに対し、１．０ＮのＮａＯＨ水溶液を、通液速度（液空間速度）ＳＶが４ｈｒ－１となるように７０分間通水し、官能基のイオン形を全てＮａ形に変換した。
その後、０．５０ＮのＨＣｌ水溶液を、通液速度ＳＶが８ｈｒ－１となるように７０分間通水し、官能基のイオン形を全てＨ形に変換した。
この後、Ｈ形に変換した樹脂に対し、超純水を液空間速度ＳＶが５０ｈｒ－１となるように通水し、得られた処理水の比抵抗値（ＭΩ・ｃｍ）を測定した。その結果を表１に示す。
Example 1
A 1.0 N aqueous NaOH solution was passed through a column packed with 500 mL (500 mL-R) of weakly acidic cation exchange resin (AMBERLITE HPR8400-HG, manufactured by Organo Corporation) for 70 minutes at a flow rate (liquid hourly space velocity) SV of 4 hr -1 , thereby converting all of the ionic forms of the functional groups to the Na form.
Thereafter, a 0.50N HCl aqueous solution was passed through the column for 70 minutes at a flow rate SV of 8 hr -1 to convert all of the ionic forms of the functional groups into the H-form.
Thereafter, ultrapure water was passed through the H-type resin at a liquid hourly space velocity (SV) of 50 hr -1 , and the resistivity (MΩ·cm) of the resulting treated water was measured. The results are shown in Table 1.
（実施例２～３、比較例１～２）
ＨＣｌ水溶液の規定度を０．５０Ｎ、通液速度ＳＶを８ｈｒ－１とすることに代えて、表１に記載の通りの規定度及び通液速度とすること以外は、実施例１と同様に行った。その結果を表１に示す。
(Examples 2 to 3, Comparative Examples 1 to 2)
The same procedure as in Example 1 was repeated, except that the normality and flow rate of the HCl aqueous solution were changed to those shown in Table 1, instead of changing the normality to 0.50 N and the flow rate SV to 8 hr -1 . The results are shown in Table 1.
なお、実施例１～３及び比較例１では、再生工程で通液したＨＣｌ水溶液の規定度、通液速度及び通液時間より、十分に再生された。 In addition, in Examples 1 to 3 and Comparative Example 1, the normality, flow rate, and flow time of the aqueous HCl solution passed through in the regeneration process were sufficient to result in sufficient regeneration.
Claims (3)
Ｈ形に変換されたＨ形陽イオン交換樹脂に洗浄水を接触させることにより、該Ｈ形陽イオン交換樹脂を洗浄する洗浄工程と、
を有すること、
該陽イオン交換樹脂は、弱酸性陽イオン交換樹脂であり、
該酸水溶液の規定度が、０．１０～０．５０Ｎであること、
該酸水溶液を、ＳＶ８～４０ｈ -1 の通液速度で通液することにより、該再生工程を行うこと、
該再生工程における、該酸水溶液の規定度Ａと、該酸水溶液の通液速度Ｂの関係が、下記式（１）：
Ａ×Ｂ≦４．５（１）
（式中、Ａは、酸水溶液の規定度（Ｎ）であり、Ｂは、酸水溶液の通液速度ＳＶ（ｈ -1 ）である。）
を満たすこと、
を特徴とする陽イオン交換樹脂の調整方法。 a regeneration step of converting the cation exchange resin to the H-form by contacting the cation exchange resin with an aqueous acid solution;
a washing step of washing the H-form cation exchange resin by contacting the H-form cation exchange resin converted to the H-form with wash water;
having
The cation exchange resin is a weakly acidic cation exchange resin,
The normality of the aqueous acid solution is 0.10 to 0.50N;
The regeneration step is carried out by passing the aqueous acid solution through the column at a flow rate of SV8 to 40 h -1.
In the regeneration step, the relationship between the normality A of the aqueous acid solution and the flow rate B of the aqueous acid solution is expressed by the following formula (1):
A × B ≦ 4.5 (1)
(In the formula, A is the normality (N) of the acid aqueous solution, and B is the flow rate SV (h −1 ) of the acid aqueous solution.)
To satisfy the following:
A method for preparing a cation exchange resin, comprising the steps of:
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| JP3417244B2 (en) * | 1997-02-19 | 2003-06-16 | 栗田工業株式会社 | Regeneration method of ion exchange resin |
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| JP2005218947A (en) | 2004-02-05 | 2005-08-18 | Kanai Hiroaki | Ion removal cartridge filter and method of manufacturing the same |
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