JP3992299B2 - Ultrapure water production equipment - Google Patents
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- JP3992299B2 JP3992299B2 JP22469194A JP22469194A JP3992299B2 JP 3992299 B2 JP3992299 B2 JP 3992299B2 JP 22469194 A JP22469194 A JP 22469194A JP 22469194 A JP22469194 A JP 22469194A JP 3992299 B2 JP3992299 B2 JP 3992299B2
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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
- Y02A20/131—Reverse-osmosis
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- Removal Of Specific Substances (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は超純水製造装置に係り、特に、従来の超純水製造装置では除去困難なホウ酸性ホウ素を効果的に除去することにより、高純度超純水を安定に得ることを可能とする超純水製造装置に関する。
【０００２】
【従来の技術】
従来、市水、地下水、工水等の原水から超純水を製造する超純水製造装置は、基本的に、前処理装置、一次純水製造装置及び二次純水製造装置から構成される。このうち、前処理装置は、凝集、浮上、濾過装置で構成される。一次純水製造装置は、２基の逆浸透膜分離装置及び混床式イオン交換装置、或いは、イオン交換純水装置及び逆浸透膜分離装置で構成され、また、二次純水製造装置は、低圧紫外線酸化装置、混床式イオン交換装置及び限外濾過膜分離装置で構成される。
【０００３】
これらの各装置単位において、原水の脱塩は、逆浸透膜分離装置及び混床式イオン交換装置で行われる。また、原水中の微粒子の除去は、逆浸透膜分離装置及び限外濾過膜分離装置でなされ、原水中のＴＯＣ成分の除去は、逆浸透膜分離装置、イオン交換純水装置、低圧紫外線酸化装置でなされる。
【０００４】
【発明が解決しようとする課題】
上記従来の超純水製造装置により工水、その他の水を原水として超純水を製造する場合、得られる超純水の純度が悪く、管理値を満足し得ない場合がある。例えば、抵抗率１８．２４μΩ・ｃｍの超純水を製造する超純水製造装置において、得られる超純水の抵抗率が１７．８μΩ・ｃｍあるいはそれ以下にまで低下する場合がある。このような純度低下は、特に、装置内のイオン交換樹脂の使用時間が長くなった場合に著しい。
【０００５】
この問題を解決するために、強塩基性アニオン交換樹脂の量を増やす、樹脂の再生レベルを変える、などの対策を講じても、顕著な改善効果は得られなかった。
【０００６】
本発明者らは上記従来の超純水製造装置における純度低下の問題を解決し、高純度の超純水を安定に得ることができる超純水製造装置を提供することを目的とする。
【０００７】
請求項１の超純水製造装置は、脱塩装置を有する一次純水製造装置と、二次純水製造装置とを有する超純水製造装置において、該脱塩装置の後段の一次純水製造装置内に、鉱酸で再生後ＯＨ形に変換したホウ素吸着樹脂を充填したホウ素吸着樹脂塔を設けたことを特徴とする。
請求項２の超純水製造装置は、請求項１において、該脱塩装置として逆浸透膜分離装置を２段に設け、該２段に設けた逆浸透膜分離装置の後段に前記ホウ素吸着樹脂塔を設けたことを特徴とする。
請求項３の超純水製造装置は、脱塩装置を有する一次純水製造装置と、二次純水製造装置とを有する超純水製造装置において、該脱塩装置として逆浸透膜分離装置を２段に設け、該２段に設けた逆浸透膜分離装置の後段の一次純水製造装置内にホウ素吸着樹脂塔を設けたことを特徴とする。
【０００８】
即ち、本発明者らは、従来の超純水製造装置における純度低下の原因を究明すべく鋭意検討を重ねた結果、純度低下の原因はホウ素であることを突き止めた。
【０００９】
そして、このホウ素の除去のためには、脱塩装置の後段の一次純水製造装置内にホウ素吸着樹脂塔を設けることが有効であることを見出し、本発明を完成させた。
【００１０】
以下に本発明を詳細に説明する。
【００１１】
本発明において、ホウ素吸着樹脂としては、各種のものを用いることができるが、例えば、市販の「ダイヤイオンＣＲＢ０２」（三菱化成（株））を用いることができる。このダイヤイオンＣＲＢ０２は、以下に示す如く、スチレン・ジビニルベンゼンの骨格にホウ酸選択性の高いキレート形成基としてＮグルカミン基を導入した化学構造を有している。
【００１２】
【化１】
このＮグルカミン基は、弱塩基性アニオン交換樹脂と同様の３級アミン型になっており、次のような反応でホウ酸性ホウ素を吸着する。
【００１４】
【化２】
ところで、このＮグルカミン基は、Ｃｌ- やＳＯ4 2- を吸着した場合には、ホウ酸の吸着能がなくなる。中性塩、例えばＮａＣｌが共存する場合、これらの塩に対するホウ素吸着樹脂の交換容量は全交換容量の２０％程度あり、次のような反応でＣｌ- イオンを吸着するため、その分、ホウ素の交換容量が低減する。即ち、系内の塩濃度が高い場合には、ホウ素吸着樹脂のホウ素吸着能は約２０％程度低下することとなる。
【００１６】
【化３】
従って、本発明においては、逆浸透膜分離装置又はイオン交換純水装置等の脱塩装置の後段にホウ素吸着樹脂塔を設け、ホウ素吸着樹脂塔への塩類の流入を防止することにより、高いホウ素吸着能を確保する。
【００１８】
なお、処理を継続することにより、ダイヤイオンＣＲＢ０２の吸着容量が飽和に達し、ホウ素吸着能が低下した場合には、下記の如く、Ｈ2 ＳＯ4 等の鉱酸で再生し、ホウ酸（或いは更に塩酸）を脱着させた後、ＮａＯＨでＯＨ- 形に変換することにより、再度使用に供することができる。
【００１９】
【化４】
なお、ホウ素吸着樹脂をＳＯ4 2- 形又はＣｌ- 形で使用することも考えられるが、ＳＯ4 2- 形又はＣｌ- 形のものは中性の水に対してはホウ素吸着性能が悪い。アルカリ性の水に対してはホウ素吸着性能が若干向上するものの、吸着容量はＯＨ- 形で使用する場合に比べて小さい。
【００２１】
このため、本発明においては、ホウ素吸着樹脂の塩形はＯＨ- 形として用いるのが好ましい。
【００２２】
このようなホウ素吸着樹脂を充填したホウ素吸着樹脂塔への通水速度が高くなると、ホウ酸吸着量が低減するため、通水速度は流入水のホウ素濃度、ホウ素吸着樹脂のホウ酸吸着量及び使用期間等を考慮してＳＶ＝５〜５０ｈｒ-1の範囲で適宜決定するのが好ましい。
【００２３】
前述の如く、本発明の超純水製造装置において、ホウ素吸着樹脂塔は、一次純水製造装置内の脱塩を行う装置の後段であれば良く、その設置箇所としては特に制限はない。
【００２４】
即ち、吸着除去の対象であるホウ酸性ホウ素は、中性ないしそれ以下のｐＨ条件では、Ｈ3 ＢＯ3 として存在している。通常の超純水系ではその濃度も低く、ｐＨ条件も中性付近にあることから、一次脱塩した後では、ホウ素は同一挙動をとるため、ホウ素吸着樹脂塔はどの箇所に設置してもホウ素の除去性能に差はない。
【００２５】
本発明に好適なホウ素吸着樹脂塔の設置例を以下に示す。なお、以下において、各々の略号は次のものを示す。
【００２６】
ＡＦ：凝集濾過装置
ＲＯ：逆浸透膜分離装置
ＭＢ−Ｐ：混床式イオン交換塔
２Ｂ３Ｔ：２床３塔式イオン交換純水装置
ＳＴ：サブタンク
Ｌ−ＵＶＯＸ：低圧紫外線酸化装置
ＤＩ：混床式イオン交換装置
ＵＦ：限外濾過膜分離装置
［ＢＡ］：ホウ素吸着樹脂塔
Ｉ 下記（ａ）又は（ｂ）の通常の超純水製造装置の一次純水製造装置に適用する場合
（ａ） 原水→ＡＦ→一次純水製造装置（ＲＯ→ＲＯ→ＭＢ−Ｐ）→ＳＴ→二次純水製造装置（Ｌ−ＵＶＯＸ→ＤＩ→ＵＦ）→ユースポイント又はＳＴ返送
（ｂ） 原水→一次純水製造装置（ＡＦ→２Ｂ３Ｔ→ＭＢ−Ｐ→ＲＯ）→ＳＴ→二次純水製造装置（Ｌ−ＵＶＯＸ→ＤＩ→ＵＦ）→ユースポイント又はＳＴ返送
(1) 原水→ＡＦ→ＲＯ→ＲＯ→［ＢＡ］→ＭＢ−Ｐ→ＳＴ→二次純水製造装置
(2) 原水→ＡＦ→ＲＯ→ＲＯ→ＭＢ−Ｐ→［ＢＡ］→ＳＴ→二次純水製造装置
(3) 原水→ＡＦ→２Ｂ３Ｔ→［ＢＡ］→ＭＢ−Ｐ→ＲＯ→ＳＴ→二次純水製造装置
(4) 原水→ＡＦ→２Ｂ３Ｔ→ＭＢ−Ｐ→［ＢＡ］→ＲＯ→ＳＴ→二次純水製造装置
(5) 原水→ＡＦ→２Ｂ３Ｔ→ＭＢ−Ｐ→ＲＯ→［ＢＡ］→ＳＴ→二次純水製造装置
【００２７】
【作用】
原水中にホウ酸性ホウ素が存在する場合、或いは、回収水を超純水の原水として利用する系において回収水中にホウ酸が含有される場合、従来の超純水製造装置ではこれらのホウ素を除去することができず、或いは、アニオン交換樹脂が新品ないし再生直後においては除去可能であっても、その後早期に除去不可能となる。これは、前述の如く、系内のホウ素の存在形態がＨ3 ＢＯ3 として存在していることによるものである。一方、本発明の場合ホウ素吸着樹脂は高アルカリ性（ｐＨ９以上）となっているので、Ｈ3 ＢＯ3 は塔内で下記反応式に従って、水和して解離し、イオン交換可能となる。
【００２８】
Ｈ3 ＢＯ3 ＋Ｈ2 Ｏ → Ｂ（ＯＨ）4 -＋Ｈ+
このようなことから、従来の超純水製造装置において、アニオン交換樹脂の量を増やしたり、樹脂の再生レベルを変えたりしても、顕著な効果は得られず、製造される超純水中には、１ｐｐｂないしそれ以上のホウ素濃度のホウ酸のリークがある。これにより、得られる超純水の抵抗率の低下が見られる。
【００２９】
本発明の超純水製造装置では、この従来の超純水製造装置では除去し得ない、従って、従来の超純水製造装置の純度低下の原因物質であるホウ素を、ホウ素吸着樹脂塔により効率的に除去するため、高純度の超純水を安定に得ることができる。
【００３０】
しかして、このホウ素吸着樹脂塔は、脱塩装置の後段に設置されるため、塩類の共存により、ホウ素吸着樹脂のホウ素の吸着能が阻害されることなく、高いホウ素除去効率を得ることができる。
【００３１】
また、ホウ素吸着樹脂はＳｉＯ2 除去能力をも有し、従って、ホウ素吸着樹脂塔を組み込むことにより、後段の装置に対するＳｉＯ2 負荷の軽減を図ることもできる。
【００３２】
【実施例】
以下に実施例及び比較例を挙げて、本発明をより具体的に説明する。説明の便宜上、まず比較例を挙げる。
【００３３】
なお、以下の実施例及び比較例において、処理に供した原水は、ホウ酸性ホウ素（Ｂ（ＯＨ）4 -−Ｂ）濃度約１００ｐｐｂのものである。
【００３４】
比較例１
原水をＡＦ→２Ｂ３Ｔ→ＭＢ−Ｐ→ＳＴ→Ｌ−ＵＶOX→ＤＩ→ＵＦの順で通水して処理したところ、得られた処理水（ＵＦ流出水）のＢ（ＯＨ）4 -−Ｂ濃度は２〜３ｐｐｂであり、ホウ素の残留が認められた。
【００３５】
実施例１
比較例１において、ホウ素吸着樹脂としてダイヤイオンＣＲＢ０２を充填したホウ素吸着樹脂をＭＢ−Ｐの後段に組み込み、比較例１で処理した原水と同水質の原水をＡＦ→２Ｂ３Ｔ→ＭＢ−Ｐ→［ＢＡ］→ＳＴ→Ｌ−ＵＶOX→ＤＩ→ＵＦに順次通水して処理した。
【００３６】
なお、ホウ素吸着樹脂ダイヤイオンＣＲＢ０２は、樹脂塔カラムに１リットル充填し、５重量％ＨＣｌを１００ｇ−ＨＣｌ／リットル−樹脂の割合で用いて押出洗浄した後、４重量％ＮａＯＨを１００ｇ−ＮａＯＨ／リットル−樹脂の割合で用いて押出洗浄して用いた。また、ホウ素吸着樹脂塔の通水速度はＳＶ＝２０ｈｒ-1とした。
【００３７】
その結果、ホウ素吸着樹脂塔の流入水及び流出水のホウ素濃度，ＳｉＯ2 濃度は表１に示す通りであり、ホウ素及びＳｉＯ2 を効率的に除去することができた。なお、この処理を３ケ月継続した後もホウ素及びＳｉＯ2 の除去効果に差はなく、長期にわたり継続処理可能であることが確認された。
【００３８】
【表１】
比較例２
実施例１において、ホウ素吸着樹脂塔の代りに強塩基性ＯＨ形アニオン交換樹脂塔（三菱化成（株）製「ダイヤイオンＳＡＮ−ＵＰ」（新品）を１リットル充填）を設けたこと以外は同様にして処理を行った。
【００４０】
その結果、アニオン交換樹脂塔の流出水のホウ素濃度は表２に示す如く、経時的に増加し、長期継続処理ができないことが判明した。
【００４１】
【表２】
実施例２
前記(1)の処理工程において、実施例１で設けたものと同様のホウ素吸着樹脂塔を適用して同様に処理を行った。即ち、原水→ＡＦ→ＲＯ→ＲＯ→［ＢＡ］→ＭＢ−Ｐ→ＳＴ→二次純水製造装置の順で処理した。その結果、得られた超純水（ＵＦ流出水）の抵抗率は３ケ月継続処理後においても１８．１μΩ・ｃｍ以上と高い純度を示した。
【００４３】
また、この処理において、ホウ素吸着樹脂塔の流入水及び流出水のホウ素濃度を調べたところ、流入水のＢ（ＯＨ）4 -−Ｂは２０〜３０ｐｐｂであるのに対し、流出水のＢ（ＯＨ）4 -−Ｂは＜０．０５ｐｐｂであり、ホウ素が効率的に除去されたことが確認された。
【００４４】
比較例３
実施例２において、ホウ素吸着樹脂塔を設けなかったこと以外は同様に処理を行った。即ち、原水→ＡＦ→ＲＯ→ＲＯ→ＭＢ−Ｐ→ＳＴ→二次純水製造装置の順で処理した。この処理において、ＭＢ−Ｐの流入水及び流出水のホウ素濃度を調べたところ、流入水のＢ（ＯＨ）４ −−Ｂは２０〜３０ｐｐｂであるのに対し、流出水のＢ（ＯＨ）４ −−Ｂは７ｐｐｂと、ホウ素のリークが認められた。
【００４５】
【発明の効果】
以上詳述した通り、本発明の超純水製造装置によれば、従来の超純水製造装置では除去し得ない、超純水の純度低下の原因物質であるホウ素を効率的に除去することができ、高純度の超純水を安定かつ効率的に得ることが可能とされる。しかも、本発明に係るホウ素吸着樹脂塔では、ＳｉＯ2 の除去もなされ、後段の装置へのＳｉＯ2 負荷が軽減されるという効果も奏される。[0001]
[Industrial application fields]
The present invention relates to an ultrapure water production apparatus, and in particular, it is possible to stably obtain high-purity ultrapure water by effectively removing boric acid boron, which is difficult to remove with a conventional ultrapure water production apparatus. It relates to ultrapure water production equipment.
[0002]
[Prior art]
Conventionally, an ultrapure water production apparatus that produces ultrapure water from raw water such as city water, groundwater, and industrial water basically includes a pretreatment apparatus, a primary pure water production apparatus, and a secondary pure water production apparatus. . Among these, the pretreatment device is composed of agglomeration, levitation, and filtration devices. The primary pure water production apparatus is composed of two reverse osmosis membrane separation devices and a mixed bed type ion exchange device, or an ion exchange pure water device and a reverse osmosis membrane separation device. It consists of a low-pressure ultraviolet oxidizer, a mixed bed ion exchanger and an ultrafiltration membrane separator.
[0003]
In each of these apparatus units, the raw water is desalted by a reverse osmosis membrane separation apparatus and a mixed bed ion exchange apparatus. The removal of fine particles in the raw water is performed by a reverse osmosis membrane separation device and an ultrafiltration membrane separation device, and the removal of the TOC component in the raw water is performed by a reverse osmosis membrane separation device, an ion exchange pure water device, a low-pressure ultraviolet oxidation device. Made in
[0004]
[Problems to be solved by the invention]
When ultrapure water is produced by using the above-described conventional ultrapure water production apparatus using industrial water or other water as raw water, the purity of the obtained ultrapure water may be poor and the control value may not be satisfied. For example, in an ultrapure water production apparatus that produces ultrapure water having a resistivity of 18.24 μΩ · cm, the resistivity of the obtained ultrapure water may be reduced to 17.8 μΩ · cm or less. Such a decrease in purity is particularly remarkable when the use time of the ion exchange resin in the apparatus becomes long.
[0005]
In order to solve this problem, even if measures such as increasing the amount of strongly basic anion exchange resin or changing the regeneration level of the resin were taken, a remarkable improvement effect could not be obtained.
[0006]
An object of the present invention is to provide an ultrapure water production apparatus capable of solving the problem of purity reduction in the conventional ultrapure water production apparatus and capable of stably obtaining high-purity ultrapure water.
[0007]
Ultrapure water production apparatus according to claim 1, a primary pure water production system having a demineralizer, the ultrapure water production apparatus and a secondary pure water producing device, primary pure water production of the subsequent desalting device The apparatus is characterized in that a boron adsorption resin tower filled with a boron adsorption resin which has been regenerated with mineral acid and converted into OH form is provided in the apparatus.
The ultrapure water production apparatus according to claim 2 is the ultrapure water production apparatus according to claim 1, wherein a reverse osmosis membrane separation device is provided in two stages as the desalting device, and the boron adsorption resin is provided in the rear stage of the reverse osmosis membrane separation device provided in the two stages. A tower is provided.
The ultrapure water production apparatus according to claim 3 is an ultrapure water production apparatus having a primary pure water production apparatus having a desalination apparatus and a secondary pure water production apparatus, wherein a reverse osmosis membrane separation apparatus is used as the demineralization apparatus. A boron-adsorbing resin tower is provided in the primary pure water production apparatus in the subsequent stage of the reverse osmosis membrane separation apparatus provided in the two stages.
[0008]
That is, as a result of intensive studies to investigate the cause of the purity decrease in the conventional ultrapure water production apparatus, the present inventors have found that the cause of the purity decrease is boron.
[0009]
And in order to remove this boron, it discovered that it was effective to provide a boron adsorption resin tower in the primary pure water manufacturing apparatus of the back | latter stage of a desalination apparatus, and completed this invention.
[0010]
The present invention is described in detail below.
[0011]
In the present invention, various types of boron adsorbent resins can be used. For example, commercially available “Diaion CRB02” (Mitsubishi Kasei Co., Ltd.) can be used. This Diaion CRB02 has a chemical structure in which an N-glucamine group is introduced as a chelate-forming group having high boric acid selectivity into the styrene-divinylbenzene skeleton as shown below.
[0012]
[Chemical 1]
This N-glucamine group is a tertiary amine type similar to the weakly basic anion exchange resin, and adsorbs boric acid boron by the following reaction.
[0014]
[Chemical 2]
Incidentally, the N glucamine group, Cl - when or adsorbed SO 4 2-a, the adsorption ability of boric acid free. When a neutral salt such as NaCl coexists, the exchange capacity of the boron adsorption resin for these salts is about 20% of the total exchange capacity, and Cl − ions are adsorbed by the following reaction. The exchange capacity is reduced. That is, when the salt concentration in the system is high, the boron adsorption capacity of the boron adsorption resin is reduced by about 20%.
[0016]
[Chemical 3]
Therefore, in the present invention, a boron adsorption resin tower is provided at the rear stage of a desalination apparatus such as a reverse osmosis membrane separation apparatus or an ion exchange deionized water apparatus to prevent the inflow of salts into the boron adsorption resin tower, thereby increasing the boron content. Ensure adsorption capacity.
[0018]
If the adsorption capacity of Diaion CRB02 reaches saturation and the boron adsorption capacity decreases by continuing the treatment, it is regenerated with a mineral acid such as H 2 SO 4 as described below, and boric acid (or Furthermore, after desorption of hydrochloric acid), it can be used again by converting it to OH - form with NaOH.
[0019]
[Formula 4]
Incidentally, boron adsorption resin SO 4 2-form or Cl - it is conceivable to use in the form, SO 4 2-form or Cl - forms of the above boron adsorption performance is poor against neutral water. Although the boron adsorption performance is slightly improved for alkaline water, the adsorption capacity is smaller than that in the case of using the OH - form.
[0021]
Therefore, in the present invention, the salt form of the boron adsorption resin is preferably used as the OH - form.
[0022]
When the water flow rate to the boron adsorption resin tower filled with such boron adsorption resin is increased, the boric acid adsorption amount is reduced. Therefore, the water flow rate is determined based on the boron concentration of the inflow water, the boric acid adsorption amount of the boron adsorption resin, and It is preferable to appropriately determine in the range of SV = 5 to 50 hr −1 in consideration of the period of use and the like.
[0023]
As described above, in the ultrapure water production apparatus of the present invention, the boron adsorption resin tower may be a subsequent stage of the desalting apparatus in the primary pure water production apparatus, and the installation location is not particularly limited.
[0024]
In other words, boric acid boron, which is the target of adsorption removal, exists as H 3 BO 3 under neutral or lower pH conditions. In normal ultrapure water systems, the concentration is low and the pH condition is near neutral. Therefore, after primary desalting, boron behaves in the same way. There is no difference in the removal performance.
[0025]
An installation example of a boron adsorption resin tower suitable for the present invention is shown below. In the following, each abbreviation indicates the following.
[0026]
AF: aggregation filtration device RO: reverse osmosis membrane separation apparatus MB-P: mixed bed ion exchange column 2B3T: 2 bed 3-tower ion exchange pure water device ST: subtank L-UV OX: low pressure ultraviolet oxidation equipment
D I: mixed-bed ion exchanger UF: ultrafiltration membrane separation equipment
[ BA]: Boron adsorption resin tower I When applied to the primary pure water production apparatus of the following normal ultrapure water production apparatus (a) or (b) (a) Raw water → AF → primary pure water production apparatus (RO → RO → MB-P) → ST → secondary pure water production equipment (L-UV OX → DI → UF) → use point or ST return (b) Raw water → primary pure water production equipment (AF → 2B3T → MB-P → RO) → ST → Secondary pure water production equipment (L-UV OX → DI → UF) → Use point or ST return
(1) Raw water → AF → RO → RO → [BA] → MB-P → ST → secondary pure water production apparatus
(2) Raw water → AF → RO → RO → MB-P → [BA] → ST → secondary pure water production equipment
(3) Raw water → AF → 2B3T → [BA] → MB-P → RO → ST → secondary pure water production equipment
(4) Raw water → AF → 2B3T → MB-P → [BA] → RO → ST → secondary pure water production equipment
(5) Raw water → AF → 2B3T → MB-P → RO → [BA] → ST → secondary pure water production apparatus
[Action]
When boric acid boron is present in the raw water, or when boric acid is contained in the recovered water in a system that uses the recovered water as the raw water of ultrapure water, the conventional ultrapure water production apparatus removes these boron. However, even if the anion exchange resin is new or can be removed immediately after regeneration, it cannot be removed early. This is due to the presence of boron in the system as H 3 BO 3 as described above. On the other hand, in the case of the present invention, since the boron adsorption resin is highly alkaline (pH 9 or more), H 3 BO 3 is hydrated and dissociated in the tower according to the following reaction formula, and ion exchange becomes possible.
[0028]
H 3 BO 3 + H 2 O → B (OH) 4 − + H +
For this reason, in the conventional ultrapure water production apparatus, even if the amount of anion exchange resin is increased or the regeneration level of the resin is changed, a remarkable effect cannot be obtained. Leaks boric acid with a boron concentration of 1 ppb or more. Thereby, the fall of the resistivity of the obtained ultrapure water is seen.
[0029]
In the ultrapure water production apparatus of the present invention, this conventional ultrapure water production apparatus cannot remove it. Therefore, boron, which is a causative substance of the purity reduction of the conventional ultrapure water production apparatus, is more efficiently absorbed by the boron adsorption resin tower. Therefore, highly pure ultrapure water can be obtained stably.
[0030]
Therefore, since this boron adsorption resin tower is installed in the latter stage of the desalting apparatus, high boron removal efficiency can be obtained without inhibiting the boron adsorption ability of the boron adsorption resin due to the coexistence of salts. .
[0031]
Further, the boron adsorbing resin also has a SiO 2 removal capability. Therefore, by incorporating a boron adsorbing resin tower, it is possible to reduce the SiO 2 load on the downstream apparatus.
[0032]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. For convenience of explanation, a comparative example is given first.
[0033]
In the following examples and comparative examples, the raw water subjected to the treatment has a boric acid boron (B (OH) 4 − —B) concentration of about 100 ppb.
[0034]
Comparative Example 1
When raw water was treated by passing in order of AF → 2B3T → MB-P → ST → L-UV OX → DI → UF, B (OH) 4 − −B of the obtained treated water (UF effluent) The concentration was 2 to 3 ppb, and boron residue was observed.
[0035]
Example 1
In Comparative Example 1, a boron adsorbing resin filled with Diaion CRB02 as a boron adsorbing resin was incorporated in the latter stage of MB-P, and the raw water of the same water quality as the raw water treated in Comparative Example 1 was AF → 2B3T → MB-P → [BA ] → ST → L-UV OX → DI → UF was passed through in order.
[0036]
Boron adsorption resin Diaion CRB02 was filled in 1 liter in a resin tower column, extruded and washed using 5 wt% HCl at a ratio of 100 g-HCl / liter-resin, and then 4 wt% NaOH was added in 100 g-NaOH / Used in a ratio of liter-resin and washed by extrusion. Further, the water flow rate of the boron adsorption resin tower was set to SV = 20 hr −1 .
[0037]
As a result, the boron concentration and SiO 2 concentration of inflow water and outflow water of the boron adsorption resin tower were as shown in Table 1, and boron and SiO 2 could be efficiently removed. Even after this treatment was continued for 3 months, there was no difference in the effect of removing boron and SiO 2 , and it was confirmed that the treatment could be continued for a long time.
[0038]
[Table 1]
Comparative Example 2
Example 1 is the same as Example 1 except that a strongly basic OH type anion exchange resin tower (filled with 1 liter of “Diaion SAN-UP” (new) manufactured by Mitsubishi Kasei Co., Ltd.) is provided instead of the boron adsorption resin tower. The process was carried out.
[0040]
As a result, it was found that the boron concentration of the effluent of the anion exchange resin tower increased with time as shown in Table 2, and long-term continuous treatment was impossible.
[0041]
[Table 2]
Example 2
In the treatment step (1) , the same treatment was performed by applying the same boron adsorption resin tower as that provided in Example 1. That is, it processed in order of raw | natural water->AF->RO->RO->[BA]->MB-P->ST-> secondary pure water manufacturing apparatus . As a result, the resistivity of the obtained ultrapure water (UF effluent) showed a high purity of 18.1 μΩ · cm or more even after 3 months of continuous treatment.
[0043]
In this treatment, the boron concentration of the inflow water and outflow water of the boron adsorption resin tower was examined, and the inflow water B (OH) 4 − −B was 20 to 30 ppb, whereas the outflow water B ( OH) 4 − —B was <0.05 ppb, confirming that boron was efficiently removed.
[0044]
Comparative Example 3
In Example 2, the treatment was performed in the same manner except that the boron adsorption resin tower was not provided. That is, processing was performed in the order of raw water → AF → RO → RO → MB-P → ST → secondary pure water production apparatus . In this treatment, when the boron concentration of the influent and effluent of MB-P was examined, B (OH) 4 − −B of the influent water was 20 to 30 ppb, whereas B (OH) 4 of the effluent water - -B is a 7ppb, leakage of boron was observed.
[0045]
【The invention's effect】
As described above in detail, according to the ultrapure water production apparatus of the present invention, it is possible to efficiently remove boron, which is a causative substance of the purity reduction of ultrapure water, which cannot be removed by the conventional ultrapure water production apparatus. It is possible to obtain highly pure ultrapure water stably and efficiently. Moreover, in the boron adsorption resin tower according to the present invention, SiO 2 is removed, and the effect of reducing the SiO 2 load on the subsequent apparatus is also achieved.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22469194A JP3992299B2 (en) | 1994-09-20 | 1994-09-20 | Ultrapure water production equipment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22469194A JP3992299B2 (en) | 1994-09-20 | 1994-09-20 | Ultrapure water production equipment |
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| Publication Number | Publication Date |
|---|---|
| JPH0889956A JPH0889956A (en) | 1996-04-09 |
| JP3992299B2 true JP3992299B2 (en) | 2007-10-17 |
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| JP22469194A Expired - Fee Related JP3992299B2 (en) | 1994-09-20 | 1994-09-20 | Ultrapure water production equipment |
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| US11156041B2 (en) * | 2012-02-22 | 2021-10-26 | Richard Paul Posa | System and method for treating water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3426072B2 (en) * | 1996-01-17 | 2003-07-14 | オルガノ株式会社 | Ultrapure water production equipment |
| JP4599803B2 (en) * | 2002-04-05 | 2010-12-15 | 栗田工業株式会社 | Demineralized water production equipment |
| JP3864934B2 (en) | 2003-06-12 | 2007-01-10 | 栗田工業株式会社 | Pure water production equipment |
| WO2006134915A1 (en) | 2005-06-14 | 2006-12-21 | Asahi Kasei Chemicals Corporation | Apparatus for water treatment and method of treating water |
| JP5320723B2 (en) * | 2007-11-06 | 2013-10-23 | 栗田工業株式会社 | Ultrapure water manufacturing method and apparatus, and electronic component member cleaning method and apparatus |
| JP5081690B2 (en) * | 2008-03-31 | 2012-11-28 | オルガノ株式会社 | Production method of ultra pure water |
| WO2010089877A1 (en) * | 2009-02-06 | 2010-08-12 | 赤穂化成株式会社 | Process for producing mineral drinking water, apparatus for producing mineral drinking water, and drinking water obtained by the process |
| JP5564817B2 (en) * | 2009-03-31 | 2014-08-06 | 栗田工業株式会社 | Ion exchange resin regeneration method and ultrapure water production apparatus |
| JP6082192B2 (en) * | 2012-06-11 | 2017-02-15 | 野村マイクロ・サイエンス株式会社 | Pure water production equipment |
| CA3006319A1 (en) * | 2016-01-25 | 2017-08-03 | Kurion, Inc. | System and method for manipulation of ion concentration to maximize efficiency of ion exchange |
| JP2023127080A (en) * | 2022-03-01 | 2023-09-13 | オルガノ株式会社 | Ultrapure water production system and ultrapure water production method |
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| US11156041B2 (en) * | 2012-02-22 | 2021-10-26 | Richard Paul Posa | System and method for treating water |
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