JPH08224580A - Acid removing apparatus, pure water producing apparatus provided therewith, and weakly basic anion-exchange resin for acid removal - Google Patents
Acid removing apparatus, pure water producing apparatus provided therewith, and weakly basic anion-exchange resin for acid removalInfo
- Publication number
- JPH08224580A JPH08224580A JP7032515A JP3251595A JPH08224580A JP H08224580 A JPH08224580 A JP H08224580A JP 7032515 A JP7032515 A JP 7032515A JP 3251595 A JP3251595 A JP 3251595A JP H08224580 A JPH08224580 A JP H08224580A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- exchange resin
- anion exchange
- basic anion
- weakly basic
- 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.)
- Pending
Links
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、酸成分を含有する廃水
から、あるいは前段においてＨ形の陽イオン交換樹脂に
よって脱カチオンされた酸性の水や糖液等の液体から酸
成分を除去する装置および該装置を備えた純水製造装
置、並びにこれらの装置に用いられる酸除去用弱塩基性
陰イオン交換樹脂に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a device for removing an acid component from wastewater containing an acid component or from a liquid such as acidic water or sugar solution decationized by an H-type cation exchange resin in the preceding stage. The present invention also relates to a pure water producing apparatus equipped with the apparatus, and a weakly basic anion exchange resin for acid removal used in these apparatuses.
【０００２】[0002]
【従来の技術】廃水等から酸成分を除去する装置として
は、従来、弱塩基性陰イオン交換樹脂を塔やカラムに充
填したものが用いられている。2. Description of the Related Art As a device for removing an acid component from wastewater, a column or column packed with a weakly basic anion exchange resin has been used.
【０００３】弱塩基性陰イオン交換樹脂の官能基は第一
〜第三級アミノ基であり、水中での解離は弱く、中性塩
分解反応はほとんど起こらないが、酸を効率良く吸着す
る。また、弱塩基性陰イオン交換樹脂は、再生効率もよ
いので、酸の除去や、純水製造装置の陽イオン交換塔の
後段に強塩基性陰イオン交換樹脂と併用して用いられて
いる。The functional group of the weakly basic anion exchange resin is a primary to tertiary amino group, its dissociation in water is weak, and a neutral salt decomposition reaction hardly occurs, but it efficiently adsorbs an acid. Further, since the weakly basic anion exchange resin has good regeneration efficiency, it is used in combination with the strongly basic anion exchange resin in the subsequent stage of the acid removal and the cation exchange column of the pure water producing apparatus.
【０００４】弱塩基性陰イオン交換樹脂の母体として、
主にスチレン−ジビニルベンゼン共重合体またはアクリ
ル−ジビニルベンゼン共重合体が用いられている。As a matrix of weakly basic anion exchange resin,
A styrene-divinylbenzene copolymer or an acryl-divinylbenzene copolymer is mainly used.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、アクリ
ル酸および／またはその誘導体とジビニルベンゼンの共
重合体を母体とする弱塩基性陰イオン交換樹脂（以下
「アクリル系弱塩基性陰イオン交換樹脂」と略称する）
は、母体の性質上高いイオン交換容量を有しているが、
アルカリ通薬後の洗浄性が悪いため、再生に用いたアル
カリを洗浄して再使用可能となる所定の水質にするまで
に多量の洗浄水が必要となる。アクリル系弱塩基性陰イ
オン交換樹脂において、アルカリ再生後の洗浄性が悪い
のは、母体のアクリル−ジビニルベンゼン共重合体の骨
格に存在するＣ＝Ｏ基の一部が、使用中に加水分解され
て−ＣＯＯ-基となり、この−ＣＯＯ-基が再生剤のＮａ
ＯＨと接触することにより−ＣＯＯＮａとなり、この−
ＣＯＯＮａが洗浄時加水分解され、Ｎａ+がリークする
ためである。However, a weakly basic anion exchange resin (hereinafter referred to as "acrylic weakly basic anion exchange resin") having a copolymer of acrylic acid and / or its derivative and divinylbenzene as a matrix is used. (Abbreviated)
Has a high ion exchange capacity due to the nature of the matrix,
Since the washability after the alkaline solution is poor, a large amount of wash water is required before washing the alkali used for regeneration to a predetermined water quality that enables reuse. In the acrylic weakly basic anion exchange resin, the detergency after alkali regeneration is poor because a part of the C═O group existing in the skeleton of the base acrylic-divinylbenzene copolymer is hydrolyzed during use. Is converted into a —COO − group, and the —COO − group is used as the regenerant Na.
When it comes into contact with OH, it becomes -COONa.
This is because COONa is hydrolyzed during washing and Na + leaks.
【０００６】一方スチレン−ジビニルベンゼン共重合体
を母体とする弱塩基性陰イオン交換樹脂（以下「スチレ
ン系弱塩基性陰イオン交換樹脂」と略称する）は、アル
カリ通薬後の洗浄性は良好であるが、母体の性質上、ア
クリル系弱塩基性陰イオン交換樹脂よりもイオン交換容
量が少ないため、一定量の被処理液を処理するのに多量
の樹脂が必要となる。そのため、スチレン系弱塩基性陰
イオン交換樹脂を用いた酸除去装置を大きくしなければ
ならない。On the other hand, a weakly basic anion exchange resin having a styrene-divinylbenzene copolymer as a base material (hereinafter abbreviated as "styrene-based weakly basic anion exchange resin") has good detergency after an alkaline passage. However, due to the nature of the matrix, it has a smaller ion exchange capacity than the acrylic weakly basic anion exchange resin, so a large amount of resin is required to treat a certain amount of the liquid to be treated. Therefore, the acid removing device using the styrene-based weakly basic anion exchange resin must be enlarged.
【０００７】従って、酸除去装置を製造するには、樹脂
量と洗浄水量のバランスを考えて、アクリル系弱塩基性
陰イオン交換樹脂またはスチレン系弱塩基性陰イオン交
換樹脂を使い分けるか、アクリル系弱塩基性陰イオン交
換樹脂を用いる場合は、リークするＮａＯＨを除去する
ために後段に陽イオン交換塔を設置すること等が行われ
ている。Therefore, in order to manufacture an acid removing device, considering the balance between the amount of resin and the amount of washing water, either an acrylic weak base anion exchange resin or a styrene weak base anion exchange resin is used properly, or an acrylic base is used. When a weakly basic anion exchange resin is used, a cation exchange column is installed in the subsequent stage in order to remove leaking NaOH.
【０００８】本発明の課題は、上記従来の弱塩基性陰イ
オン交換樹脂を充填した酸除去装置の欠点を解消し、交
換容量が高く、再生時の洗浄性に優れ、かつ再生効率の
良好な酸除去装置及びこのような酸除去装置を備えた純
水製造装置、並びにこれらの装置に用いられる弱塩基性
陰イオン交換樹脂を提供することにある。The object of the present invention is to solve the above-mentioned drawbacks of the conventional acid removing apparatus filled with a weakly basic anion exchange resin, to have a high exchange capacity, to be excellent in cleaning property at the time of regeneration, and to have a good regeneration efficiency. An object of the present invention is to provide an acid removing device, a pure water producing device equipped with such an acid removing device, and a weakly basic anion exchange resin used in these devices.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、上記課題
を解決すべく鋭意研究を重ねた結果、アクリル系弱塩基
性陰イオン交換樹脂において、一定の範囲で第四級アン
モニウム基を導入したイオン交換樹脂を用いることによ
り上記課題が解消されることを見いだし、本発明を完成
するに至った。As a result of intensive studies to solve the above problems, the present inventors have introduced a quaternary ammonium group in a certain range in an acrylic weakly basic anion exchange resin. It has been found that the above problems can be solved by using the above ion exchange resin, and the present invention has been completed.
【００１０】すなわち、本発明は、全イオン交換容量あ
たり１０〜３０当量％が第四級アンモニウム基である
（メタ）アクリル−ジビニルベンゼン共重合体を母体と
する弱塩基性陰イオン交換樹脂を充填したことを特徴と
する酸除去装置及び当該酸除去装置を備えてなる純水製
造装置並びに全イオン交換容量あたり１０〜３０当量％
が第四級アンモニウム基である（メタ）アクリル−ジビ
ニルベンゼン共重合体を母体とする酸除去用弱塩基性陰
イオン交換樹脂に関するものである。That is, according to the present invention, a weakly basic anion exchange resin having a (meth) acryl-divinylbenzene copolymer, which is a quaternary ammonium group in an amount of 10 to 30 equivalent% based on the total ion exchange capacity, as a base is filled. The acid removing device, the pure water producing device including the acid removing device, and 10 to 30 equivalent% based on the total ion exchange capacity
Relates to a weakly basic anion exchange resin for acid removal, which has a (meth) acrylic-divinylbenzene copolymer having a quaternary ammonium group as a base.
【００１１】本発明の１０〜３０当量％が第四級アンモ
ニウム基を有する（メタ）アクリル−ジビニルベンゼン
共重合体を母体とする弱塩基性陰イオン交換樹脂は、構
成モノビニル単量体単位としての（メタ）アクリル部位
および構成ポリビニル単量体単位としてジビニルベンゼ
ンより構成される。そして、モノビニル単量体単位の
（メタ）アクリル部位に、弱塩基性官能基が導入された
ものであるが、本発明の場合には、強塩基性官能基であ
る第四級アンモニウム基が１０〜３０当量％導入された
ものである。The weakly basic anion exchange resin having a (meth) acryl-divinylbenzene copolymer of which 10 to 30 equivalent% has a quaternary ammonium group as a matrix of the present invention has a monovinyl monomer unit as a constituent. (Meth) acrylic moiety and composed of divinylbenzene as a constituent polyvinyl monomer unit. Then, a weakly basic functional group is introduced into the (meth) acrylic portion of the monovinyl monomer unit. In the case of the present invention, the quaternary ammonium group which is a strongly basic functional group is 10 ˜30 equivalent% was introduced.
【００１２】その製造方法は、公知の方法に従うが、具
体的に例示すれば、（メタ）アクリル酸もしくはそれら
のアルキルエステル等のモノビニル単量体とポリビニル
単量体のジビニルベンゼンを共重合させ、次いでこの共
重合体にポリアルキレンポリアミンを反応させることに
よって、弱塩基性陰イオン交換樹脂が得られる。次い
で、これに１０〜３０当量％の第四級アンモニウム基が
導入されるように、メチルクロライド等のハロゲン化ア
ルキル、ギ酸とホルマリン、エチレンクロルヒドリン等
のアルキレンハロゲノヒドリン等の第四級化剤を反応さ
せることにより本発明の陰イオン交換樹脂が容易に得ら
れる。The method for its production is in accordance with a known method. Specifically, a monovinyl monomer such as (meth) acrylic acid or an alkyl ester thereof is copolymerized with divinylbenzene as a polyvinyl monomer. Then, a weakly basic anion exchange resin is obtained by reacting this copolymer with a polyalkylene polyamine. Then, a quaternization of alkyl halide such as methyl chloride, formic acid and formalin, alkylene halogenohydrin such as ethylene chlorohydrin, etc. is performed so that 10 to 30 equivalent% of a quaternary ammonium group is introduced. By reacting the agent, the anion exchange resin of the present invention can be easily obtained.
【００１３】なお、本発明の共重合体母体にあっては、
他のモノビニル単量体、例えば、スチレン、エチルスチ
レン、ビニルトルエン等を本発明の陰イオン交換樹脂の
性能を変えない範囲において共重合させることもできる
し、また、ポリビニル単量体として、例えば、ジビニル
ナフタレン、ジビニルトルエン、トリビニルベンゼン、
ジ（メタ）アクリル酸エチレングリコールエステル、ト
リメチロールプロパントリ（メタ）アクリレート等も同
様に共重合させることができる。In the copolymer matrix of the present invention,
Other monovinyl monomers, for example, styrene, ethylstyrene, vinyltoluene and the like can be copolymerized within a range that does not change the performance of the anion exchange resin of the present invention, and as a polyvinyl monomer, for example, Divinylnaphthalene, divinyltoluene, trivinylbenzene,
Di (meth) acrylic acid ethylene glycol ester, trimethylolpropane tri (meth) acrylate and the like can be copolymerized in the same manner.
【００１４】本発明の酸除去装置に用いられる弱塩基性
陰イオン交換樹脂は、第一〜第三級アミノ基等の弱塩基
性の陰イオン交換基を全イオン交換容量当り７０〜９０
当量％、好ましくは８０〜９０当量％とし、第四級アン
モニウム基からなる強塩基性の陰イオン交換基を１０〜
３０当量％、好ましくは１０〜２０当量％としたことを
特徴とするものである。第四級アンモニウム基が１０当
量％未満では、再生時の洗浄性が悪く、３０当量％を超
えると再生効率が低くなるため好ましくない。なお、上
記第四級アンモニウム基からなる強塩基性陰イオン交換
基の当量％とは、全イオン交換容量に対する強塩基性陰
イオン交換基の交換容量（すなわち、中性塩分解容量）
の割合として定義されるもので、具体的には以下の測定
方法、あるいはこれに準ずる方法によって求めたもので
ある。The weakly basic anion exchange resin used in the acid removing apparatus of the present invention contains weakly basic anion exchange groups such as primary to tertiary amino groups in an amount of 70 to 90 per total ion exchange capacity.
Equivalent%, preferably 80 to 90 equivalent%, and 10 to 10 strongly basic anion exchange groups consisting of quaternary ammonium groups.
It is characterized in that it is 30 equivalent%, preferably 10 to 20 equivalent%. If the quaternary ammonium group is less than 10 equivalent%, the detergency during regeneration is poor, and if it exceeds 30 equivalent%, the regeneration efficiency is lowered, which is not preferable. The equivalent% of the strongly basic anion exchange group consisting of the quaternary ammonium group is the exchange capacity of the strongly basic anion exchange group with respect to the total ion exchange capacity (ie, neutral salt decomposition capacity).
Is determined by the following measurement method or a method equivalent thereto.
【００１５】（測定方法）再生型の陰イオン交換樹脂の
体積を正しく測りとり（１０ｍＬ〜１５ｍＬ）カラムに
充填する。これに５００ｍＬの１Ｎ塩酸溶液を９〜１０
ｍＬ／ｍｉｎで通水し、陰イオン交換樹脂の交換基を総
てＣｌ-形に変換する。これをエタノールで十分洗浄し
た後、０．１５ｍｏｌ／Ｌのアンモニア水２５０ｍＬを
９〜１０ｍＬ／ｍｉｎで通水し、流出液を集液し、引き
続き２５０ｍＬの純水で洗浄しこれも共に集液し、Ａ液
とする。(Measurement method) The volume of the regenerated anion exchange resin is accurately measured (10 mL to 15 mL) and packed in a column. To this, add 500 mL of 1N hydrochloric acid solution to 9 to 10
All the exchange groups of the anion exchange resin are converted to the Cl − form by passing water at mL / min. After thoroughly washing this with ethanol, 250 mL of 0.15 mol / L ammonia water was passed at 9 to 10 mL / min to collect the effluent, followed by washing with 250 mL of pure water to collect both together. , Liquid A.
【００１６】再び、純水で洗浄した後、１Ｎの硝酸ナト
リウム溶液５００ｍＬを通液し、流出液を集液して、Ｂ
液とするＡ液中のＣｌ-濃度を分析し、単位樹脂体積あ
たりの樹脂から脱離したＣｌ-量（Ｃｌ-の当量）を求
め、Ｘｍｅｑ／ｍＬ−Ｒとする。After washing again with pure water, 500 mL of a 1N sodium nitrate solution was passed through to collect the effluent, and
The Cl − concentration in the liquid A, which is a liquid, is analyzed, and the amount of Cl − desorbed from the resin per unit resin volume (equivalent amount of Cl − ) is obtained and defined as Xmeq / mL-R.
【００１７】Ｂ液中のＣｌ-濃度とＯＨ-濃度を分析し、
単位樹脂体積あたりのＣｌ-およびＯＨ-の脱離量を求
め、Ｃｌ-の脱離量をＹｍｅｑ／ｍＬ−Ｒ、ＯＨ-の脱離
量をＺｍｅｑ／ｍＬ−Ｒとする。[0017] Cl of B solution - analyzing the concentration - concentration and OH
The desorbed amounts of Cl − and OH − per unit resin volume are obtained, and the desorbed amount of Cl − is Ymeq / mL-R and the desorbed amount of OH − is Zmeq / mL-R.
【００１８】上記、Ｘ，Ｙ，Ｚの値から、全イオン交換
容量（Ｔ−Ｃａｐ）、強塩基性陰イオン交換基のイオン
交換容量（ＳＢ−Ｃａｐ）、および弱塩基性陰イオン交
換基のイオン交換容量（ＷＢ−Ｃａｐ）は次式のごとく
表される。From the above X, Y and Z values, the total ion exchange capacity (T-Cap), the ion exchange capacity of the strongly basic anion exchange group (SB-Cap), and the weakly basic anion exchange group are calculated. The ion exchange capacity (WB-Cap) is expressed by the following equation.
【００１９】 Ｔ−Ｃａｐ＝（Ｙ＋Ｘ）（ｍｅｑ／ｍＬ−Ｒ） ＳＢ−Ｃａｐ＝（Ｙ＋Ｚ）（ｍｅｑ／ｍＬ−Ｒ） ＷＢ−Ｃａｐ＝（Ｘ−Ｚ）（ｍｅｑ／ｍＬ−Ｒ） したがって、強塩基性陰イオン交換基の当量％（ＳＢ
％）は、下記式によって求められる。T-Cap = (Y + X) (meq / mL-R) SB-Cap = (Y + Z) (meq / mL-R) WB-Cap = (XZ) (meq / mL-R) Therefore, strong Equivalent% of basic anion exchange group (SB
%) Is calculated by the following formula.
【００２０】[0020]
【数１】 [Equation 1]
【００２１】本発明の酸除去装置で除去できる酸として
は、塩酸、硫酸、硝酸、フッ酸等の鉱酸や、酢酸、ぎ酸
等の有機酸である。Acids that can be removed by the acid removing apparatus of the present invention include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid, and organic acids such as acetic acid and formic acid.
【００２２】本発明の酸除去装置は、上記の弱塩基性陰
イオン交換樹脂を、塔やカラムに充填したものである。
酸成分を含有する廃水や、純水あるいは超純水の製造工
程におけるＨ形の陽イオン交換樹脂によって脱カチオン
化された酸性の水や糖液等の液体から酸成分を除去する
ために用いることができる。本発明の酸除去装置は、陽
イオン交換樹脂を用いた陽イオン交換樹脂塔と組合わせ
て２床３塔形、３床４塔形、４床５塔形等の複床式純水
製造装置や、複層床式純水製造装置に用いることができ
る。複層床式純水製造装置に用いる場合は、上記の弱塩
基性陰イオン交換樹脂と強塩基性陰イオン交換樹脂を同
一の塔に充填した酸除去装置を陰イオン交換塔として用
いればよい。The acid removing apparatus of the present invention is a column or column packed with the above-mentioned weakly basic anion exchange resin.
Use to remove acid components from wastewater containing acid components, acidic water deionized by H-type cation exchange resin in the production process of pure water or ultrapure water, or liquid such as sugar solution You can The acid removing apparatus of the present invention is a multi-bed pure water producing apparatus such as a two-bed, three-column type, a three-bed, four-column type, a four-bed, five-column type in combination with a cation exchange resin tower using a cation exchange resin. Alternatively, it can be used in a multi-layer bed type pure water producing apparatus. When used in a multi-layer bed pure water producing apparatus, the acid removing apparatus in which the weak basic anion exchange resin and the strong basic anion exchange resin are packed in the same tower may be used as the anion exchange tower.
【００２３】[0023]
【作用】本発明の酸除去装置の再生時の洗浄性がよい理
由としては、本発明の酸除去装置に用いる弱塩基性陰イ
オン交換樹脂は交換基の一部が第四級アンモニウム基で
あるため、母体の−ＣＯＯ-と第四級アンモニウム基
が樹脂内で塩を形成し、再生時の−ＣＯＯＮａの生成を
抑制する、第四級アンモニウム基はプラスの電荷を有
しているので、Ｎａ+イオンとの静電的な反発により樹
脂層内へのＮａ+イオンの拡散を抑制し、そのため−Ｃ
ＯＯＮａの生成が抑えられる、第四級アンモニウム基
は弱塩基***換基に比べ親水性が高く、洗浄されやすい
等のことが考えられる。The reason why the acid removing apparatus of the present invention has good cleaning performance during regeneration is that the weakly basic anion exchange resin used in the acid removing apparatus of the present invention has some of the exchange groups as quaternary ammonium groups. Therefore, the base —COO − and the quaternary ammonium group form a salt in the resin, and suppress the production of —COONa during regeneration. The quaternary ammonium group has a positive charge, so It suppresses the diffusion of Na + ions into the resin layer by electrostatic repulsion with + ions, and therefore -C
It is considered that the formation of OONa is suppressed, the quaternary ammonium group has higher hydrophilicity than the weakly basic exchange group, and is easily washed.
【００２４】[0024]
【実施例】本発明の酸除去装置を、純水製造装置に用い
た場合の、一例を図１に示す。EXAMPLE FIG. 1 shows an example in which the acid removing apparatus of the present invention is used in a pure water producing apparatus.
【００２５】図１は、３床４塔形純水製造装置に本発明
の酸除去装置を用いた場合のフロー図であり、１はＨ形
強酸性陽イオン交換樹脂を充填した陽イオン交換塔、２
は脱炭酸塔、３は本発明の酸除去装置、４は強塩基性陰
イオン交換樹脂を充填した陰イオン交換塔である。FIG. 1 is a flow chart when the acid removing apparatus of the present invention is used in a 3-bed, 4-tower type pure water producing apparatus, and 1 is a cation exchange column filled with H-type strong acid cation exchange resin. Two
Is a decarbonation tower, 3 is an acid removing apparatus of the present invention, and 4 is an anion exchange tower filled with a strongly basic anion exchange resin.
【００２６】原水が図１の実線で示したごとく陽イオン
交換塔１を通過すると、原水中に含まれるＣａ2+，Ｍｇ
2+，Ｎａ+等の陽イオンが水素イオンと交換され酸性の
水となり、次いで、脱炭酸塔２を通過すると、前記酸性
水中の二酸化炭素が除去され、さらに本発明の酸除去装
置３を通過すると酸性水中の鉱酸成分（Ｃｌ-，ＳＯ2- 4
等）が吸着され、最後に陰イオン交換塔４でシリカおよ
び残余の陰イオンが除去されて純水となる。When the raw water passes through the cation exchange tower 1 as shown by the solid line in FIG. 1, Ca 2+ , Mg contained in the raw water
The cations such as 2+ and Na + are exchanged with hydrogen ions to become acidic water. Then, when passing through the decarbonation tower 2, carbon dioxide in the acidic water is removed and further passed through the acid removing device 3 of the present invention. Then the acidic water mineral components (Cl -, SO 2- 4
Etc.) is adsorbed, and finally silica and residual anions are removed in the anion exchange tower 4 to obtain pure water.
【００２７】上述のような純水の製造を所定時間行っ
て、純水の製造量が規定量に達したり、あるいは規定の
純度の純水が得られなくなったりして、いわゆる通水終
点に達した場合には、陽イオン交換塔１、酸除去装置３
および陰イオン交換塔４を常法により再生する。After the pure water as described above is produced for a predetermined time, the amount of pure water produced reaches a specified amount, or pure water having a specified purity cannot be obtained, and the so-called water passing end point is reached. If so, cation exchange tower 1, acid removal device 3
And the anion exchange column 4 is regenerated by a conventional method.
【００２８】すなわち、陽イオン交換塔１に対しては、
点線で示したごとく塩酸または硫酸水溶液等の酸を通薬
して再生し、一方、酸除去装置３および陰イオン交換塔
に対しては、水酸化ナトリウム水溶液等のアルカリを、
点線で示したごとく陰イオン交換塔、酸除去装置３の順
に通薬することによって陰イオン交換塔４および酸除去
装置３を再生する。上記酸通薬およびアルカリ通薬後、
各イオン交換塔および酸除去装置に純水等の水を流して
残留する酸、アルカリを洗浄し、洗浄終了後、再び、前
述したような純水の製造を行う。That is, for the cation exchange tower 1,
As indicated by the dotted line, regeneration is performed by passing an acid such as hydrochloric acid or a sulfuric acid aqueous solution, while an alkali such as a sodium hydroxide aqueous solution is supplied to the acid removing device 3 and the anion exchange tower.
As shown by the dotted line, the anion exchange column 4 and the acid removing device 3 are regenerated by sequentially passing through the anion exchange column and the acid removing device 3. After the above-mentioned acid and alkaline medications,
Water such as pure water is flowed through each ion exchange tower and the acid removing device to wash the residual acid and alkali, and after the washing is finished, the pure water is again produced as described above.
【００２９】上記酸除去装置３内に充填されている陰イ
オン交換樹脂は、全イオン交換容量あたり１０〜３０当
量％が第四級アンモニウム基である（メタ）アクリル−
ジビニルベンゼン共重合体を母体とする弱塩基性陰イオ
ン交換樹脂であって、残りの７０〜９０当量％の部分は
弱塩基であるため、再生効率において、従来のアクリル
系弱塩基性陰イオン交換樹脂とほとんど同じであり、し
たがって、上記酸除去装置３は、上述のごとく、陰イオ
ン交換塔４の再生に一度使用されたアルカリ再生廃液を
使用して十分に再生することができる。さらに、イオン
交換容量的にも第四級アンモニウム基が０当量％である
従来のアクリル系弱塩基性陰イオン交換樹脂とほぼ同等
の高いイオン交換容量を有しており、したがって従来の
アクリル系陰イオン交換樹脂を使用した純水製造装置と
ほぼ同等の処理能力を得ることができる。The anion exchange resin filled in the acid removing device 3 has a (meth) acryl-containing quaternary ammonium group in an amount of 10 to 30 equivalent% based on the total ion exchange capacity.
It is a weakly basic anion exchange resin having a divinylbenzene copolymer as a matrix, and the remaining 70 to 90 equivalent% of the portion is a weak base. Since it is almost the same as the resin, the acid removing device 3 can be sufficiently regenerated by using the alkali regenerating waste liquid once used for regenerating the anion exchange column 4 as described above. Further, in terms of ion exchange capacity, it has a high ion exchange capacity almost equal to that of a conventional acrylic weakly basic anion exchange resin in which a quaternary ammonium group is 0 equivalent%, and therefore, a conventional acrylic anion exchange resin is used. It is possible to obtain almost the same processing capacity as that of a pure water producing apparatus using an ion exchange resin.
【００３０】しかも、上記酸除去装置は、第四級アンモ
ニウム基が０当量％である従来のアクリル系陰イオン交
換樹脂を使用している装置に比べて、アルカリ通薬後の
洗浄性が極めて良好であり、従来より少量の洗浄水の使
用で十分に洗浄することができる。In addition, the above-mentioned acid removing device has a very good cleaning property after the alkaline passage, as compared with a device using a conventional acrylic type anion exchange resin having a quaternary ammonium group of 0 equivalent%. Therefore, it can be sufficiently washed with a smaller amount of washing water than before.
【００３１】実験例１ アクリル樹脂製カラムに表１のイオン交換樹脂を充填
し、本発明の酸除去装置を調製した。Experimental Example 1 An acrylic resin column was filled with the ion exchange resin shown in Table 1 to prepare an acid removing apparatus of the present invention.
【００３２】[0032]
【表１】 [Table 1]
【００３３】上記酸除去装置に、原水（純水に塩酸と硫
酸を、それぞれ１００ｍｇ ａｓＣａＣＯ3／ＬＨＣ
ｌ、１００ｍｇ ａｓ ＣａＣＯ3／ＬＨ2ＳＯ4となる
ように溶解したもの）をＬＶ３０ｍ／ｈｒで充填樹脂量
の４００倍量通水した後、２ｗｔ％ＮａＯＨ水溶液を、
使用した陰イオン交換樹脂の総交換容量と等しい量（当
量）だけ通薬（通薬ＳＶ４）し、次いで樹脂量の２倍量
の純水を通水（押出し）してイオン交換樹脂の再生を行
い、その後以下のような洗浄試験と通水試験を行った。
その結果を表２に示す。In the above-mentioned acid removing device, raw water (pure water containing hydrochloric acid and sulfuric acid, respectively, 100 mg asCaCO 3 / LHC
1, dissolved in 100 mg as CaCO 3 / LH 2 SO 4 ) at LV 30 m / hr in an amount of 400 times the filling resin amount, and then a 2 wt% NaOH aqueous solution is added,
The ion exchange resin is regenerated by passing an amount (equivalent amount) equal to the total exchange capacity of the anion exchange resin used (equivalent amount SV4), and then passing (extruding) twice the amount of pure water as the amount of resin (extrusion). After that, the following cleaning test and water flow test were performed.
The results are shown in Table 2.
【００３４】（洗浄試験）純水をＳＶ１０で通水し、洗
浄廃水のｐＨを測定し、ｐＨ９になるまでに要する洗浄
水量を測定する。(Washing test) Pure water is passed through the SV10, the pH of the washing wastewater is measured, and the amount of washing water required to reach pH 9 is measured.
【００３５】（通水試験）上記洗浄終了後、上記原水を
ＬＶ３０ｍ／ｈｒで通水し、処理水の電気伝導率が１０
μＳ／ｃｍに達した点を終点としたときの処理水量を求
める。(Water Flow Test) After the above washing, the raw water was passed at LV 30 m / hr, and the electric conductivity of the treated water was 10%.
The amount of treated water is determined when the point at which μS / cm is reached is the end point.
【００３６】[0036]
【表２】 [Table 2]
【００３７】比較例１〜３ 総イオン交換容量あたりの第四級アンモニウム基が０当
量％，７当量％，３５当量％であるアクリル系弱塩基性
陰イオン交換樹脂を用いて、実施例１に準じて、酸除去
装置を調製し、実験例１と同様に洗浄試験と通水試験を
行った。その結果を表３に示す。Comparative Examples 1-3 Acrylic weakly basic anion exchange resins having quaternary ammonium groups per total ion exchange capacity of 0 equivalent%, 7 equivalent% and 35 equivalent% were used in Example 1. According to the above, an acid removing device was prepared, and a washing test and a water flow test were conducted in the same manner as in Experimental Example 1. Table 3 shows the results.
【００３８】[0038]
【表３】 [Table 3]
【００３９】表２および表３の結果から明らかなよう
に、従来の第四級アンモニウム基が０当量％であるアク
リル系弱塩基性陰イオン交換樹脂を用いた比較例１の酸
除去装置に比較して、本発明の酸除去装置は、洗浄水量
を著しく削減できることが分かる。さらに、本発明の酸
除去装置の処理水量は、上記従来の酸除去装置と同程度
であることが分かる。As is clear from the results of Tables 2 and 3, comparison with the conventional acid remover of Comparative Example 1 using an acrylic weakly basic anion exchange resin having 0 equivalent% of quaternary ammonium groups was made. Then, it can be seen that the acid removing apparatus of the present invention can significantly reduce the amount of washing water. Further, it can be seen that the treated water amount of the acid removing device of the present invention is about the same as that of the conventional acid removing device.
【００４０】一方、第四級アンモニウム基が７当量％の
アクリル系弱塩基性陰イオン交換樹脂を用いた比較例２
の酸除去装置は、洗浄性に改善が見られず、第四級アン
モニウム基が３５当量％のアクリル系弱塩基性陰イオン
交換樹脂を用いた比較例３の酸除去装置は、洗浄性は良
好なものの処理水量の低下がみられた。On the other hand, Comparative Example 2 using an acrylic weakly basic anion exchange resin containing 7 equivalent% of quaternary ammonium groups.
The acid remover of No. 3 did not show any improvement in detergency, and the acid remover of Comparative Example 3 using the acrylic weakly basic anion exchange resin having 35 equivalent% of quaternary ammonium groups had good detergency. However, the amount of treated water decreased.
【００４１】[0041]
【発明の効果】本発明の酸除去装置および該酸除去装置
を用いた純水製造装置並びに酸除去用弱塩基性陰イオン
交換樹脂は、以下のような優れた効果を有している。The acid removing apparatus, the pure water producing apparatus using the acid removing apparatus, and the weakly basic anion exchange resin for acid removal of the present invention have the following excellent effects.
【００４２】（１）再生時の洗浄性がよいため洗浄水量
を削減することができる。(1) Since the cleaning property at the time of regeneration is good, the amount of cleaning water can be reduced.
【００４３】（２）交換容量が高く、従来のアクリル系
弱塩基性陰イオン交換樹脂を用いた酸除去装置と同程度
の処理水量を確保でき、スチレン系弱塩基性陰イオン交
換樹脂に比べて使用樹脂量が少なくてすむため、装置全
体を小型化できる。(2) It has a high exchange capacity and can secure the same amount of treated water as an acid removal device using a conventional acrylic weakly basic anion exchange resin, which is higher than that of a styrene weakly basic anion exchange resin. Since the amount of resin used is small, the entire device can be downsized.
【００４４】（３）再生効率がよく、総イオン交換容量
とほぼ等しい量（理論量）のアルカリ剤の使用によって
十分に再生できる。(3) The regeneration efficiency is good, and the regeneration can be sufficiently performed by using an alkaline agent in an amount (theoretical amount) substantially equal to the total ion exchange capacity.
【図１】３床４塔形純水製造装置に本発明の酸除去装置
を用いたフロー図。FIG. 1 is a flow chart in which an acid removing device of the present invention is used in a three-bed, four-column type pure water producing device.
１ 陽イオン交換塔 ２ 脱炭酸塔 ３ 本発明の酸除去装置 ４ 陰イオン交換塔 1 Cation Exchange Tower 2 Decarbonation Tower 3 Acid Removal Device of the Present Invention 4 Anion Exchange Tower
Claims (3)
％が第四級アンモニウム基である（メタ）アクリル−ジ
ビニルベンゼン共重合体を母体とする弱塩基性陰イオン
交換樹脂を充填したことを特徴とする酸除去装置。1. A weakly basic anion exchange resin having a (meth) acryl-divinylbenzene copolymer as a matrix, which has a quaternary ammonium group content of 10 to 30 equivalent% based on the total ion exchange capacity. Acid removal equipment.
純水製造装置。2. A pure water production apparatus comprising the acid removing device according to claim 1.
％が第四級アンモニウム基である（メタ）アクリル−ジ
ビニルベンゼン共重合体を母体とする酸除去用弱塩基性
陰イオン交換樹脂。3. A weakly basic anion exchange resin for acid removal, which comprises a (meth) acryl-divinylbenzene copolymer, which has a quaternary ammonium group in an amount of 10 to 30 equivalent% based on the total ion exchange capacity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7032515A JPH08224580A (en) | 1995-02-21 | 1995-02-21 | Acid removing apparatus, pure water producing apparatus provided therewith, and weakly basic anion-exchange resin for acid removal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7032515A JPH08224580A (en) | 1995-02-21 | 1995-02-21 | Acid removing apparatus, pure water producing apparatus provided therewith, and weakly basic anion-exchange resin for acid removal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08224580A true JPH08224580A (en) | 1996-09-03 |
Family
ID=12361115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7032515A Pending JPH08224580A (en) | 1995-02-21 | 1995-02-21 | Acid removing apparatus, pure water producing apparatus provided therewith, and weakly basic anion-exchange resin for acid removal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08224580A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010519018A (en) * | 2007-02-16 | 2010-06-03 | スリーエム イノベイティブ プロパティズ カンパニー | Systems and processes for removing fluorinated chemicals from water |
| JP2012016673A (en) * | 2010-07-09 | 2012-01-26 | Japan Organo Co Ltd | Device and method of treating iodine/boron-containing solution |
| WO2018088015A1 (en) * | 2016-11-10 | 2018-05-17 | 栗田工業株式会社 | Regeneration method for multilayer anion exchange column |
-
1995
- 1995-02-21 JP JP7032515A patent/JPH08224580A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010519018A (en) * | 2007-02-16 | 2010-06-03 | スリーエム イノベイティブ プロパティズ カンパニー | Systems and processes for removing fluorinated chemicals from water |
| JP2012016673A (en) * | 2010-07-09 | 2012-01-26 | Japan Organo Co Ltd | Device and method of treating iodine/boron-containing solution |
| WO2018088015A1 (en) * | 2016-11-10 | 2018-05-17 | 栗田工業株式会社 | Regeneration method for multilayer anion exchange column |
| JP2018075537A (en) * | 2016-11-10 | 2018-05-17 | 栗田工業株式会社 | Method for regenerating multilayer type anion exchange tower |
| CN109906115A (en) * | 2016-11-10 | 2019-06-18 | 栗田工业株式会社 | The regeneration method of multi-layer anion exchange tower |
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