JP2001322811A - Device and method of purifying boron eluting solution - Google Patents
Device and method of purifying boron eluting solutionInfo
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- JP2001322811A JP2001322811A JP2000138547A JP2000138547A JP2001322811A JP 2001322811 A JP2001322811 A JP 2001322811A JP 2000138547 A JP2000138547 A JP 2000138547A JP 2000138547 A JP2000138547 A JP 2000138547A JP 2001322811 A JP2001322811 A JP 2001322811A
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- Japan
- Prior art keywords
- boron
- type
- exchange resin
- ion
- ion exchange
- 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.)
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- Treatment Of Water By Ion Exchange (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸根を含むホウ素
溶離液を精製し、固体として回収するホウ素溶離液の精
製装置及び精製方法に関する。[0001] The present invention relates to an apparatus and a method for purifying a boron eluate which purifies a boron eluate containing an acid radical and recovers the solid as a solid.
【０００２】[0002]
【従来の技術】一般にニッケルメッキ液或いはアルミ表
面処理液中にはホウ素化合物（ホウ酸等）が含まれてお
り、これらを扱う工場においてはホウ素を含有する洗浄
排水が発生する。またガラス、釉薬、アルミコンデンサ
ー等ホウ素を使用する工場においてもホウ素を含む工場
排水が発生する。ホウ素化合物は植物にとっては必須微
量元素であり、海水には４〜５ｍｇ／Ｌ程度含まれてい
ることは周知のことである。一方、ホウ素が人体に与え
る影響は必ずしも明確ではないものの、低濃度の継続摂
取において生殖機能の低下などの健康障害を起こす可能
性が指摘されている。平成１１年２月、ホウ素の環境基
準として１ｍｇ／Ｌ以下が告示され、追って排水基準も
定められることになるものと予想されるため、これらの
ホウ素を含む工程排水中のホウ素除去処理が必要とな
る。2. Description of the Related Art In general, a nickel plating solution or an aluminum surface treatment solution contains a boron compound (boric acid or the like), and a factory which handles these compounds generates cleaning wastewater containing boron. In addition, factories that use boron, such as glass, glazes, and aluminum capacitors, also generate factory wastewater containing boron. It is well known that boron compounds are essential trace elements for plants and that seawater contains about 4 to 5 mg / L. On the other hand, although the effect of boron on the human body is not always clear, it has been pointed out that continuous intake of low concentrations may cause health problems such as a decrease in reproductive function. In February 1999, 1 mg / L or less was announced as an environmental standard for boron, and it is expected that a effluent standard will be set in the future. Therefore, it is necessary to remove boron from process effluents containing these borons. Become.
【０００３】ホウ素の除去方法としては、ホウ素含有排
水にアルミニウム化合物及びカルシウム化合物を用いて
凝集沈殿によりホウ素化合物を分離除去する方法（特公
昭58-15193号公報、同59-24876号公報）或いはニッケル
メッキ洗浄排水にマグネシウム塩を添加して凝集沈殿に
よりホウ素を分離除去する方法等（平成１１年度東京都
立産業技術研究所発表会予稿集ｐ５２）が知られてい
る。しかし、ホウ素を不溶化させるために多量の薬剤を
使用する必要があり、発生汚泥も多くその処理が困難で
あるという問題がある。更にこの方法ではアルミニウ
ム、カルシウム或いはマグネシウム化合物が大量に含ま
れており、ホウ素を再利用することは不可能である。As a method for removing boron, a method of separating and removing a boron compound by coagulation precipitation using an aluminum compound and a calcium compound in a boron-containing wastewater (Japanese Patent Publication Nos. 58-15193 and 59-24876) or nickel A method of adding and removing a magnesium salt to plating washing wastewater and separating and removing boron by coagulation sedimentation (1999, Tokyo Metropolitan Industrial Technology Research Institute Presentations, p52) is known. However, it is necessary to use a large amount of chemicals in order to insolubilize boron, and there is a problem that the generated sludge is large and its treatment is difficult. Furthermore, this method contains a large amount of aluminum, calcium or magnesium compounds, so that it is impossible to reuse boron.
【０００４】またホウ素含有排水を陰イオン交換樹脂、
或いはホウ素選択吸着樹脂により吸着処理する方法も数
多く知られている（特許公報平2-32952号公報、その
他）。しかし、ホウ素含有水を、ホウ素を吸着するイオ
ン交換樹脂に通液させて処理した後、当該イオン交換樹
脂からホウ素を溶離するためには酸溶液を使用するた
め、再生した酸根を含むホウ素含有水の処理に課題を持
っている。[0004] Further, the wastewater containing boron is anion-exchange resin,
Alternatively, a number of methods for performing adsorption treatment using a boron selective adsorption resin are also known (Japanese Patent Application Laid-Open No. 2-32952, and others). However, after the boron-containing water is passed through an ion exchange resin that adsorbs boron and treated, an acid solution is used to elute boron from the ion exchange resin. Have an issue in processing.
【０００５】酸根を含むホウ酸溶離液の精製方法として
は、アルカリで中和しホウ酸と中和によって生成する塩
の混合溶液にした後ホウ酸と塩との溶解度差を利用して
分離する方法が知られているが（１２６９５の化学商品
Ｐ−１５１、無機ファインケミカルの原単位＆プロセス
中日社刊１９９０年）、この方法は工程も複雑であり、
かつ設備費も高くホウ酸の製造プラントのように規模が
大きくないと実用的ではない。[0005] As a method for purifying a boric acid eluate containing an acid radical, neutralization with an alkali is performed to form a mixed solution of boric acid and a salt formed by the neutralization, and then separation is performed by utilizing the difference in solubility between boric acid and the salt. A method is known (12695 chemical product P-151, basic unit of inorganic fine chemicals & process, published by Chunichisha, 1990).
In addition, the equipment cost is high and it is not practical unless the scale is large as in a boric acid production plant.
【０００６】また溶離液を抽出剤と接触させてホウ素を
抽出し、逆抽出剤と接触させて逆抽出させ晶析法によっ
てホウ素化合物を結晶化させる方法も知られている。
（特公平1-50476号公報）抽出剤としてはオクチレング
リコール、２−エチルヘキサノール等が知られている
が、これらは消防法で定める危険物であり火気を避ける
など取り扱いが難しい。There is also known a method in which an eluent is brought into contact with an extractant to extract boron, which is then brought into contact with a back-extractant to back-extract and crystallize a boron compound by a crystallization method.
(Examined Japanese Patent Publication No. 1-50476) Octylene glycol, 2-ethylhexanol and the like are known as extractants, but these are dangerous substances specified by the Fire Service Law and are difficult to handle such as avoiding fire.
【０００７】[0007]
【発明が解決しようとする課題】本発明は上記事情に鑑
みてなされたもので、工程が簡単で、設備費も安く、高
純度のホウ素溶液を得るための酸根を有するホウ素溶離
液の精製方法を提供することを課題とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a simple process, low equipment cost, and a method for purifying a boron eluent having an acid radical for obtaining a high-purity boron solution. The task is to provide
【０００８】[0008]
【課題を解決するための手段】本発明方法はこの課題を
解決するためになされたもので、 （１） ＯＨ型に調整したＩ型強塩基性陰イオン交換樹
脂、ＯＨ型に調整したII型強塩基性陰イオン交換樹脂、
及びＯＨ型に調整した弱塩基性陰イオン交換樹脂の群か
ら選択された陰イオン交換樹脂を充填したイオン交換塔
と、イオン交換塔内の陰イオン交換樹脂を脱液状態にす
る脱液手段とを備え、脱液状態のイオン交換塔に酸根を
含むホウ素溶離液を通液させて酸根を除去し、高純度の
ホウ酸溶液を得るようにしたことを特徴とするホウ素溶
離液の精製装置。The method of the present invention has been made to solve this problem. (1) A type I strong basic anion exchange resin adjusted to OH type, a type II adjusted to OH type Strong basic anion exchange resin,
And an ion exchange tower filled with an anion exchange resin selected from the group of weakly basic anion exchange resins adjusted to OH type, and a dewatering means for dehydrating the anion exchange resin in the ion exchange tower. A boron eluent containing an acid group is passed through a deionized ion exchange column to remove the acid group, thereby obtaining a high-purity boric acid solution.
【０００９】（２） ＯＨ型に調整したＩ型強塩基性陰
イオン交換樹脂、ＯＨ型に調整したII型強塩基性陰イオ
ン交換樹脂、及びＯＨ型に調整した弱塩基性陰イオン交
換樹脂の群から選択された陰イオン交換樹脂を充填した
イオン交換塔を脱液状態にする工程と、脱液状態のイオ
ン交換塔に酸根を含むホウ素溶離液を通液させて酸根を
除去し、高純度のホウ酸溶液を得る工程とを備えたこと
を特徴とするホウ素溶離液の精製方法。(2) Type I strong basic anion exchange resin adjusted to OH type, type II strong basic anion exchange resin adjusted to OH type, and weak basic anion exchange resin adjusted to OH type A step of dehydrating an ion-exchange tower filled with an anion-exchange resin selected from the group, and passing a boron eluent containing an acid radical through the ion-exchange tower in a de-liquefied state to remove the acid radicals, thereby achieving high purity. And obtaining a boric acid solution.
【００１０】（３） イオン交換塔に充填され、ホウ素
及び酸根を吸着した陰イオン交換樹脂に水を通液してイ
オン交換塔に残留するホウ素及び酸根を溶離する工程
と、溶離した酸根を含むホウ素をホウ素溶離液に混合す
る工程と、前記ホウ素を溶離したイオン交換塔にアルカ
リ溶液を通液してイオン交換塔に充填されたイオン交換
樹脂のイオン型をＯＨ型に調整する工程と、このイオン
交換塔を脱液状態にする工程と、脱液状態のイオン交換
塔に酸根を含むホウ素溶離液を通液させて酸根を除去
し、高純度のホウ酸溶液を得る工程とを備えたことを特
徴とする（２）に記載のホウ素溶離液の精製方法。(3) a process of passing water through an anion exchange resin packed in an ion exchange column and adsorbing boron and acid radicals to elute boron and acid radicals remaining in the ion exchange column, including the eluted acid radicals A step of mixing boron with a boron eluent, and a step of passing an alkaline solution through the ion exchange tower from which the boron has been eluted to adjust the ion type of the ion exchange resin filled in the ion exchange tower to the OH type, A step of bringing the ion exchange tower into a deionized state; and a step of passing a boron eluent containing an acid root through the ion exchange tower in the dehydrated state to remove the acid root and obtain a high-purity boric acid solution. (2) The method for purifying a boron eluate according to (2).
【００１１】なお、酸根を吸着したイオン交換塔に水を
通液してイオン交換塔に残留するホウ素及び酸根を溶離
する工程では、通常、水洗よりイオン交換樹脂に残留す
るホウ素は全量流出するが、吸着している酸根は一部し
か流出しない。In the step of passing water through the ion-exchange column having adsorbed the acid radicals to elute the boron and the acid radicals remaining in the ion-exchange column, usually, the entire amount of boron remaining in the ion-exchange resin is washed out by washing with water. However, only a part of the adsorbed acid radicals flows out.
【００１２】（４） 充填されたイオン交換塔を脱液す
る際に、その調整をタイマーにより制御し、イオン交換
塔に酸根を含むホウ素溶離液を通液させて酸根を除去す
る際は、イオン交換塔出口のｐＨが７〜１に低下する時
点を検知して、この検知信号に基づいて通液停止を制御
し、ついで、通液停止後に水洗、及びアルカリ処理によ
りイオン交換塔内に充填したイオン交換樹脂をＯＨ型に
調整する際に、その調整を積算流量により制御する
（２）または（３）に記載のホウ素溶離液の精製方法。(4) When the packed ion exchange column is drained, the adjustment is controlled by a timer, and when the boron eluent containing the acid radical is passed through the ion exchange column to remove the acid radical, the ion is removed. The point at which the pH at the outlet of the exchange tower is lowered to 7-1 is detected, and the stop of the passage of the liquid is controlled based on this detection signal. The method for purifying a boron eluate according to (2) or (3), wherein when adjusting the ion exchange resin to the OH type, the adjustment is controlled by an integrated flow rate.
【００１３】この発明において、「積算流量により制御
する」とは、積算流量制御計での制御に限定されるもの
ではなく、例えば、水及びアルカリ溶液の流速を一定に
することによりタイマーで制御する方法をも含むもので
ある。[0013] In the present invention, "control by an integrated flow rate" is not limited to control by an integrated flow rate controller, but is controlled by a timer by, for example, keeping the flow rates of water and an alkaline solution constant. It also includes a method.
【００１４】（５） （２）〜（４）のいずれかに記載
の精製方法で得られた高純度のホウ酸溶液を濃縮、結晶
化してホウ酸固体とすることを特徴とするホウ素原料の
製造方法である。(5) A boron raw material characterized in that the high-purity boric acid solution obtained by the purification method according to any one of (2) to (4) is concentrated and crystallized into a boric acid solid. It is a manufacturing method.
【００１５】本発明によれば、イオン交換塔に、酸根を
含むホウ素溶離液から酸根を除去して高純度のホウ酸溶
液を得ることができる。更に当該ホウ酸溶液は通常の濃
縮結晶化によりホウ酸結晶として、ガラス、釉薬、アル
ミコンデンサー、ニッケルめっき液等ホウ酸を使用する
工程、或いは酸化ホウ素、ボロン系合金鉄等の原料とし
て使用することができる。According to the present invention, a high purity boric acid solution can be obtained by removing an acid radical from a boron eluent containing the acid radical in an ion exchange column. Further, the boric acid solution may be used as boric acid crystals by ordinary concentration crystallization, a process using boric acid such as glass, glaze, an aluminum capacitor, a nickel plating solution, or a raw material such as boron oxide, boron-based iron alloy, or the like. Can be.
【００１６】特に、陰イオン交換樹脂を予め脱液状態に
した後、酸根を含むホウ素溶離液に通液するので、ホウ
素濃度の低下を防ぎ、且つ、ホウ素回収率を高めながら
酸根を除去し、高純度のホウ酸溶液を得ることができ
る。In particular, since the anion exchange resin is previously drained and then passed through a boron eluent containing an acid radical, the decrease in boron concentration is prevented, and the acid radical is removed while increasing the boron recovery rate. A high-purity boric acid solution can be obtained.
【００１７】なお、酸根を含むホウ素溶離液は、例え
ば、ホウ素含有水を通液して、ホウ素を吸着したＩ型若
しくはII型強塩基性陰イオン交換樹脂、弱塩基性陰イオ
ン交換樹脂、或いはＮ−メチルグルカミン基を有するホ
ウ素選択吸着樹脂を充填したイオン交換塔に酸溶液を通
液することにより生じる。The boron eluent containing an acid radical is, for example, passed through boron-containing water to adsorb boron to form a type I or type II strongly basic anion exchange resin, a weakly basic anion exchange resin, or It is generated by passing an acid solution through an ion exchange column filled with a boron selective adsorption resin having an N-methylglucamine group.
【００１８】[0018]
【発明の実施の形態】以下、本発明の実施の形態を詳細
に説明する。Embodiments of the present invention will be described below in detail.
【００１９】本発明者は、イオン交換樹脂に対するホウ
素及び種々の酸根のイオン選択性及びイオン交換樹脂の
物性を鋭意研究し、酸根を含むホウ素溶離液から酸根を
効率的に分離し、高純度のホウ酸溶液を得る精製装置及
び精製方法を開発した。すなわち、ホウ素は溶液中酸性
領域ではイオン化することなくＨ3 ＢＯ3 分子として溶
解している。従って酸根を含むホウ素溶離液のように酸
性の液をＯＨ型に調整したＩ型若しくはII型強塩基性陰
イオン交換樹脂、或いはＯＨ型に調整した弱塩基性陰イ
オン交換樹脂を充填したイオン交換塔に通液すると酸根
のみ吸着してホウ素はそのまま漏出することが明らかに
なった。処理液のｐＨは酸根が吸着されている間はアル
カリ或いは中性であるが酸根が漏出し始めると急激に低
下するため終点は容易に管理できる。The present inventors have studied diligently the ion selectivity of boron and various acid radicals with respect to the ion exchange resin and the physical properties of the ion exchange resin, and efficiently separated the acid radicals from the boron eluate containing the acid radicals to obtain a high-purity acid. A purification device and a purification method for obtaining a boric acid solution have been developed. That is, boron is dissolved as H 3 BO 3 molecule without ionization in the acidic region in the solution. Therefore, an ion-exchange resin filled with an I-type or II-type strongly basic anion exchange resin whose acidic liquid has been adjusted to the OH type, such as a boron eluent containing an acid radical, or a weakly basic anion exchange resin adjusted to the OH type When the solution was passed through the column, it was found that only the acid radicals were adsorbed and the boron leaked as it was. The pH of the treatment liquid is alkali or neutral while the acid radical is adsorbed, but drops rapidly when the acid radical starts to leak, so that the end point can be easily controlled.
【００２０】また、イオン交換塔への通液は充填された
イオン交換樹脂と液との接触しない部分の生成をなくす
ため充水状態で行うのが通常であるが、この場合、処理
液のホウ素濃度低下が避けられず、且つ、ホウ素回収率
も低いという問題がある。このため脱液状態のイオン交
換塔にダウンフローで流速を大きくして通液する、或い
はアップフローで通液することによりイオン交換樹脂と
液との接触しない部分の生成をなくしながら、ホウ素濃
度の低下を防ぎ、且つ、ホウ素回収率を高めることがで
きた。The liquid passing through the ion exchange tower is usually carried out in a water-filled state in order to eliminate the formation of a portion where the liquid does not come into contact with the charged ion exchange resin. There is a problem that a decrease in the concentration is inevitable and the boron recovery is low. Therefore, by passing the solution through the ion-exchange tower in the de-watered state at a high flow rate in the down flow, or by passing the solution in the up flow, it is possible to eliminate the formation of a portion where the ion exchange resin does not come into contact with the liquid while reducing the boron concentration. The decrease was prevented and the boron recovery was able to be increased.
【００２１】しかし、ゲル型、ポーラス型を問わずＯＨ
型に調整したＩ型若しくはII型強塩基性陰イオン交換樹
脂、或いはＯＨ型に調整した弱塩基性陰イオン交換樹脂
は粒子中に数１０％の水を含んでいるため、酸根を含む
ホウ素溶離液をＯＨ型に調整したＩ型若しくはII型強塩
基性陰イオン交換樹脂、或いはＯＨ型に調整した弱塩基
性陰イオン交換樹脂を充填したイオン交換塔を予め脱液
状態にした後酸根を含む溶離液を通液すると当該イオン
交換樹脂中にホウ素が残留することが明らかになった。
当該イオン交換樹脂をそのまま通常のアルカリ溶液で再
生すると、残存しているホウ素も流出してしまい、ホウ
素の回収率が低下してしまうとともに、当該液のホウ素
除去も必要となる。However, regardless of gel type or porous type, OH
Type I or II type strongly basic anion exchange resin adjusted to type or weak basic anion exchange resin adjusted to OH type contains several tens% of water in the particles, so boron elution including acid radicals Includes acid radicals after pre-draining an ion exchange column filled with a strongly basic anion exchange resin of type I or II whose solution has been adjusted to OH type, or a weakly basic anion exchange resin adjusted to OH type. When the eluent was passed, it became clear that boron remained in the ion exchange resin.
If the ion exchange resin is regenerated with a normal alkali solution as it is, the remaining boron also flows out, lowering the boron recovery rate and necessitating the removal of boron from the solution.
【００２２】本発明者はこれらの課題の解決方法も見出
したものである。すなわち酸根を含むホウ素溶離液をＯ
Ｈ型に調整したＩ型若しくはII型強塩基性陰イオン交換
樹脂、或いはＯＨ型に調整した弱塩基性陰イオン交換樹
脂を充填したイオン交換塔を予め脱液状態にした後酸根
を含む溶離液を通液し、引き続いて水を通液することに
より当該イオン交換樹脂に残留するホウ素を回収し当該
液は酸根を含むホウ素溶離液に混合し、再び陰イオン交
換樹脂等に通液する。この方法によって、ホウ素は高純
度のホウ酸として回収できる。The present inventor has also found a solution to these problems. That is, the boron eluent containing the acid radical is
An eluent containing an acid radical after the ion-exchange column packed with a strongly basic anion exchange resin of type I or type II adjusted to H-type or a weakly basic anion exchange resin adjusted to OH type is preliminarily drained. Then, the remaining boron in the ion-exchange resin is recovered by passing water, and the resulting solution is mixed with a boron eluent containing an acid group, and again passed through an anion-exchange resin or the like. By this method, boron can be recovered as high-purity boric acid.
【００２３】[0023]
【実施例】以下本発明の実施例について図面を参照して
具体的に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below with reference to the drawings.
【００２４】まず、図示する装置について説明すると、
この装置は、酸根を含有するホウ素溶離液タンク（１
０）と、ＮａＯＨ溶液タンク（２０）と、水タンク（３
０）とを配置し、夫々のタンクの液出口に自動バルブ
（６１）、（６２）、（６３）を設け、これらの液をそ
れぞれ液供給ポンプ（７０）によりＯＨ型に調整したＩ
型若しくはII型強塩基性陰イオン交換樹脂、或いはＯＨ
型に調整した弱塩基性陰イオン交換樹脂を充填した陰イ
オン交換塔（５０）に供給するようになっている。さら
に陰イオン交換塔（５０）の入り口側配管には陰イオン
交換樹脂を脱液状態とするための圧縮空気の供給を制御
する自動バルブ（６４）を設けている。陰イオン交換塔
（５０）の液出口には、ｐＨ制御計（ＰＨＣ）、積算流
量制御計（ＦＱＣ）が取付けられている。陰イオン交換
塔（５０）の出側は、途中で分岐され、一つは排水処理
工程に、他の一つは精製ホウ素溶離液タンク（４０）
に、残りはホウ素溶離液タンク（１０）へ戻る配管が配
設されている。夫々の配管には、自動バルブ（６７）、
（６６）、（６５）が設けられている。First, the illustrated device will be described.
This apparatus is equipped with a boron eluent tank containing an acid group (1).
0), NaOH solution tank (20) and water tank (3
0), automatic valves (61), (62), and (63) were provided at the liquid outlets of the respective tanks, and these liquids were adjusted to the OH type by the liquid supply pump (70).
Type or type II strong basic anion exchange resin, or OH
The solution is supplied to an anion exchange column (50) packed with a weakly basic anion exchange resin adjusted in a mold. Further, an automatic valve (64) for controlling the supply of compressed air for bringing the anion exchange resin into a dewatered state is provided on the inlet side pipe of the anion exchange tower (50). A pH controller (PHC) and an integrated flow controller (FQC) are attached to the liquid outlet of the anion exchange tower (50). The outlet side of the anion exchange tower (50) is branched on the way, one for the wastewater treatment step, and the other for the purified boron eluent tank (40).
In addition, a pipe is provided for returning the remainder to the boron eluent tank (10). Each valve has an automatic valve (67),
(66) and (65) are provided.
【００２５】この装置では、イオン交換塔の脱液は自動
バルブ（６４）、（６７）を開き、圧縮空気をタイマー
で制御しながら陰イオン交換塔に供給して行う。タイマ
ーの脱液終了信号を検知すると、自動バルブ（６４）、
（６７）を閉じる。次に、酸根含有ホウ素溶離液通液時
には、自動バルブ（６１）、（６５）を開き、ｐＨ制御
計によりｐＨを制御しながらホウ酸溶液を精製する。次
にｐＨが７〜１、好ましくは４に低下したのを検知する
と、自動バルブ（６１）、（６５）を閉じ、自動バルブ
（６３）、（６６）を開き、陰イオン交換塔（５０）を
水洗する。この水洗の制御は、積算流量制御計により行
い、所定の流量を検出すると、自動バルブ（６３）、
（６６）を閉じ、自動バルブ（６２）、（６７）を開
き、陰イオン交換塔（５０）をアルカリ処理する。この
アルカリ処理の制御は、積算流量制御計により行い、所
定の流量を検出すると、自動バルブ（６２）を閉じ、自
動バルブ（６３）を開き（なお、自動バルブ（６７）は
開いたまま）、陰イオン交換塔（５０）を水洗する。こ
の水洗の制御は、積算流量制御計により行なう。そし
て、所定の流量を検出すると、水洗が完了し、陰イオン
交換樹脂が再生され、再使用可能となる。表１にホウ素
溶離液の分析例を示す。また、表２に各工程でのＰＨ
Ｃ，ＦＱＣの制御を示す。In this apparatus, the liquid is removed from the ion exchange tower by opening the automatic valves (64) and (67) and supplying the compressed air to the anion exchange tower while controlling the timer with a timer. When the liquid removal end signal of the timer is detected, the automatic valve (64)
(67) is closed. Next, when the acid radical-containing boron eluent is passed, the boric acid solution is purified while opening the automatic valves (61) and (65) and controlling the pH with a pH controller. Next, when it is detected that the pH has dropped to 7-1, preferably 4, the automatic valves (61) and (65) are closed, the automatic valves (63) and (66) are opened, and the anion exchange column (50) is opened. Is washed with water. This washing control is performed by an integrated flow controller, and when a predetermined flow rate is detected, an automatic valve (63)
(66) is closed, the automatic valves (62) and (67) are opened, and the anion exchange tower (50) is alkali-treated. The control of the alkali treatment is performed by an integrated flow controller, and when a predetermined flow rate is detected, the automatic valve (62) is closed and the automatic valve (63) is opened (the automatic valve (67) remains open). The anion exchange tower (50) is washed with water. This washing control is performed by an integrated flow controller. When a predetermined flow rate is detected, washing with water is completed, the anion exchange resin is regenerated, and the resin can be reused. Table 1 shows an analysis example of the boron eluent. Table 2 shows the PH at each step.
The control of C and FQC is shown.
【００２６】［実施例１］内径３４ｍｍ、高さ１，００
０ｍｍのアクリル製カラムを用意し、ＯＨ型に調整した
弱塩基性陰イオン交換樹脂を３００ｍＬ充填する。樹脂
床にイオン交換水を流速３，０００ｍＬ／Ｈｒで１時間
通液してイオン交換樹脂に残存する薬剤を抽出、洗浄
し、圧縮空気によって脱液状態にする。その後、表１に
示す組成を示すホウ素を吸着したＮ−メチルグルカミン
基を有するホウ素選択吸着樹脂を充填したイオン交換塔
に５％硫酸塩を通液することにより再生した硫酸を含む
ホウ素溶離液を流速３，０００ｍＬ／Ｈｒで通液した。
出口水のホウ素、硫酸濃度曲線は図１のとおりであり、
処理液のｐＨが急激に低下するまでの出口水は硫酸が除
去されたホウ酸溶液であった。Example 1 Inner diameter: 34 mm, height: 1,000
A 0 mm acrylic column is prepared, and 300 mL of a weakly basic anion exchange resin adjusted to the OH type is filled. Ion-exchanged water is passed through the resin bed at a flow rate of 3,000 mL / Hr for 1 hour to extract and wash the drug remaining in the ion-exchange resin, and to make it dehydrated by compressed air. Thereafter, 5% sulfate is passed through an ion exchange tower packed with a boron selective adsorption resin having an N-methylglucamine group adsorbing boron having the composition shown in Table 1 to regenerate a boron eluate containing sulfuric acid. At a flow rate of 3,000 mL / Hr.
The boron and sulfuric acid concentration curves of the outlet water are as shown in FIG.
Outlet water until the pH of the treatment liquid rapidly dropped was a boric acid solution from which sulfuric acid had been removed.
【００２７】硫酸が漏出するまでに得られる処理液のホ
ウ素濃度は０．７７ｇ／Ｌであり、処理液中のホウ素回
収率は硫酸を含むホウ素溶離液の通液量に対し、７０％
であった。The boron concentration of the processing solution obtained before the sulfuric acid leaks out is 0.77 g / L, and the boron recovery rate in the processing solution is 70% of the flow rate of the boron eluent containing sulfuric acid.
Met.
【００２８】［比較例１］内径３４ｍｍ、高さ１，００
０ｍｍのアクリル製カラムを用意し、ＯＨ型に調整した
弱塩基性陰イオン交換樹脂を３００ｍＬ充填する。樹脂
床にイオン交換水を流速３，０００ｍＬ／Ｈｒで１時間
通液してイオン交換樹脂に残存する薬剤を抽出、洗浄す
る。その後表１に示す組成を示すホウ素を吸着したＮ−
メチルグルカミン基を有するホウ素選択吸着樹脂を充填
したイオン交換塔に５％硫酸塩を通液することにより再
生した硫酸を含むホウ素溶離液を流速３，０００ｍＬ／
Ｈｒで通液した。出口水のホウ素、硫酸濃度曲線は図２
に示すとおりであり、処理液のｐＨが低下するまでの出
口水は硫酸が除去されたホウ酸溶液であった。[Comparative Example 1] Inner diameter 34 mm, height 1,00
A 0 mm acrylic column is prepared, and 300 mL of a weakly basic anion exchange resin adjusted to the OH type is filled. Ion exchange water is passed through the resin bed at a flow rate of 3,000 mL / Hr for 1 hour to extract and wash the drug remaining in the ion exchange resin. Thereafter, N- adsorbed boron having the composition shown in Table 1
The boron eluent containing sulfuric acid regenerated by passing 5% sulfate through an ion exchange column packed with a boron selective adsorption resin having a methylglucamine group was supplied at a flow rate of 3,000 mL /
The solution was passed with Hr. Figure 2 shows the concentration curves of boron and sulfuric acid in the outlet water.
The outlet water until the pH of the treatment liquid was lowered was a boric acid solution from which sulfuric acid had been removed.
【００２９】硫酸が漏出するまでに得られる処理液のホ
ウ素濃度は０．３６ｇ／Ｌであり、処理液中のホウ素回
収率は硫酸を含むホウ素溶離液の通液量に対し、３２％
であった。The boron concentration of the processing solution obtained before the sulfuric acid leaks is 0.36 g / L, and the boron recovery rate in the processing solution is 32% of the flow rate of the boron eluent containing sulfuric acid.
Met.
【００３０】［実施例２］内径３４ｍｍ、高さ１，００
０ｍｍのアクリル製カラムを用意し、ＯＨ型に調整した
弱塩基性陰イオン交換樹脂を３００ｍＬ充填する。樹脂
床にイオン交換水を流速３，０００ｍＬ／Ｈｒで１時間
通液してイオン交換樹脂に残存する薬剤を抽出、洗浄
し、圧縮空気によって脱液状態にする。その後表１に示
す組成を示すホウ素を吸着したＮ−メチルグルカミン基
を有するホウ素選択吸着樹脂を充填したイオン交換塔に
５％硫酸塩を通液することにより再生した硫酸を含むホ
ウ素溶離液を流速３，０００ｍＬ／Ｈｒで通液した。漏
出曲線は図３に示すが、処理液のｐＨが低下する時点で
の溶離液の通液を停止し、水を流速３，０００ｍＬ／Ｈ
ｒで通液する。この溶離液はホウ素の他に硫酸を含むた
め溶離液に戻して、硫酸除去原液として使用する。Example 2 Inner diameter 34 mm, height 1,00
A 0 mm acrylic column is prepared, and 300 mL of a weakly basic anion exchange resin adjusted to the OH type is filled. Ion-exchanged water is passed through the resin bed at a flow rate of 3,000 mL / Hr for 1 hour to extract and wash the drug remaining in the ion-exchange resin, and to make it dehydrated by compressed air. Thereafter, 5% sulfate was passed through an ion exchange column packed with a boron selective adsorption resin having an N-methylglucamine group adsorbing boron having the composition shown in Table 1 to obtain a regenerated sulfuric acid-containing boron eluate. The solution was passed at a flow rate of 3,000 mL / Hr. The leakage curve is shown in FIG.
Pass through with r. Since this eluate contains sulfuric acid in addition to boron, it is returned to the eluent and used as a stock solution for removing sulfuric acid.
【００３１】硫酸が漏出するまでに得られる処理液のホ
ウ素濃度は０．７６ｇ／Ｌであり、処理液中のホウ素回
収率は硫酸を含むホウ素溶離液の通液量に対し、７６％
であった。また水洗においては約６００ｍＬ通液するこ
とによりイオン交換樹脂に残留するホウ素は全量回収さ
れ、硫酸を含むホウ素溶離液に混合し、再びＯＨ型に調
整した弱塩基性陰イオン交換樹脂に通液して硫酸を除去
する。The boron concentration of the processing solution obtained before the sulfuric acid leaks out is 0.76 g / L, and the boron recovery rate in the processing solution is 76% of the flow rate of the boron eluent containing sulfuric acid.
Met. In addition, in washing with water, the entire amount of boron remaining in the ion exchange resin is recovered by passing about 600 mL, mixed with a boron eluent containing sulfuric acid, and again passed through a weakly basic anion exchange resin adjusted to OH type. To remove sulfuric acid.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【表２】 [Table 2]
【００３４】[0034]
【発明の効果】以上説明したように、本発明によれば、
脱液状態に調整した、ＯＨ型に調整したＩ型若しくはII
型強塩基性陰イオン交換樹脂、或いはＯＨ型に調整した
弱塩基性陰イオン交換樹脂を充填したイオン交換塔に、
酸根を含むホウ素溶離液を通液することにより、処理液
のホウ素濃度低下を少なくし、且つホウ素回収率も高い
状態で酸根のみを吸着し、高純度のホウ酸溶液として回
収することができる。As described above, according to the present invention,
I or II adjusted to OH type adjusted to drained state
Type strongly basic anion exchange resin, or an ion exchange column packed with a weakly basic anion exchange resin adjusted to OH type,
By passing a boron eluent containing an acid radical through, a decrease in the boron concentration of the treatment solution is reduced, and only the acid radical is adsorbed in a state where the boron recovery rate is high, so that a high-purity boric acid solution can be recovered.
【図１】実施例１の出口水のホウ素、硫酸濃度及びｐＨ
曲線を示す図。FIG. 1 shows boron, sulfuric acid concentration and pH of outlet water of Example 1.
The figure which shows a curve.
【図２】比較例1の出口水のホウ素、硫酸濃度及びｐＨ
曲線を示す図。FIG. 2 Boron, sulfuric acid concentration and pH of outlet water of Comparative Example 1
The figure which shows a curve.
【図３】実施例２の出口水のホウ素、硫酸濃度及びｐＨ
曲線を示す図。FIG. 3 shows boron, sulfuric acid concentration and pH of outlet water of Example 2.
The figure which shows a curve.
【図４】本発明装置の説明図。FIG. 4 is an explanatory view of the device of the present invention.
１０…酸根を含有するホウ素溶離液タンク、 ２０…ＮａＯＨ溶液タンク、 ３０…水タンク、 ４０…精製ホウ酸溶液タンク、 ５０…陰イオン交換塔、 ６１〜６７…自動バルブ、 ７０…液供給ポンプ、 ＰＨＣ…ｐＨ制御計、 ＦＱＣ…積算流量制御計、 タイマー…時間制御計。 Reference Signs List 10: Boron eluent tank containing acid radicals, 20: NaOH solution tank, 30: Water tank, 40: Purified boric acid solution tank, 50: Anion exchange tower, 61-67: Automatic valve, 70: Liquid supply pump, PHC: pH controller, FQC: Integrated flow controller, Timer: Time controller.
Claims (5)
交換樹脂、ＯＨ型に調整したII型強塩基性陰イオン交換
樹脂、及びＯＨ型に調整した弱塩基性陰イオン交換樹脂
の群から選択された陰イオン交換樹脂を充填したイオン
交換塔と、イオン交換塔内の陰イオン交換樹脂を脱液状
態にする脱液手段とを備え、脱液状態のイオン交換塔に
酸根を含むホウ素溶離液を通液させて酸根を除去し、高
純度のホウ酸溶液を得るようにしたことを特徴とするホ
ウ素溶離液の精製装置。1. Group of strongly basic anion exchange resins of type I adjusted to OH type, strongly basic anion exchange resins of type II adjusted to OH type, and weakly basic anion exchange resins adjusted to OH type An ion-exchange column filled with an anion-exchange resin selected from the group consisting of: and an ionic-exchange resin in the ion-exchange column. An apparatus for purifying a boron eluent, wherein the eluent is passed to remove acid radicals to obtain a high-purity boric acid solution.
交換樹脂、ＯＨ型に調整したII型強塩基性陰イオン交換
樹脂、及びＯＨ型に調整した弱塩基性陰イオン交換樹脂
の群から選択された陰イオン交換樹脂を充填したイオン
交換塔を脱液状態にする工程と、脱液状態のイオン交換
塔に酸根を含むホウ素溶離液を通液させて酸根を除去
し、高純度のホウ酸溶液をを溶離する工程と、溶離した
酸根を含むホウ素をホウ素溶離液に混合す得る工程とを
備えたことを特徴とするホウ素溶離液の精製方法。2. Group of strongly basic anion exchange resin of type I adjusted to OH type, strongly basic anion exchange resin of type II adjusted to OH type, and weakly basic anion exchange resin adjusted to OH type A step of desorbing the ion-exchange tower filled with an anion exchange resin selected from the above, and passing a boron eluent containing an acid root through the deionized ion-exchange tower to remove the acid roots, thereby obtaining a high-purity A method for purifying a boron eluate, comprising: a step of eluting a boric acid solution; and a step of mixing boron containing the eluted acid radical with the boron eluent.
根を吸着した陰イオン交換樹脂に水を通液してイオン交
換塔に残留するホウ素及び酸根る工程と、前記ホウ素を
溶離したイオン交換塔にアルカリ溶液を通液してイオン
交換塔に充填されたイオン交換樹脂のイオン型をＯＨ型
に調整する工程と、このイオン交換塔を脱液状態にする
工程と、脱液状態のイオン交換塔に酸根を含むホウ素溶
離液を通液させて酸根を除去し、高純度のホウ酸溶液を
得る工程とを備えたことを特徴とする請求項２に記載の
ホウ素溶離液の精製方法。3. A process in which water is passed through an anion exchange resin packed in an ion exchange column and adsorbing boron and acid radicals, to remove boron and acid radicals remaining in the ion exchange column, and an ion exchange column eluted with boron. Adjusting the ion type of the ion exchange resin filled in the ion exchange tower to the OH type by passing the alkaline solution through the OH type, setting the ion exchange tower in a de-watered state, and removing the ion exchange tower in a de-watered state. 3. A method for purifying a boron eluate according to claim 2, further comprising the step of: passing a boron eluent containing an acid radical through the column to remove the acid radical to obtain a high-purity boric acid solution.
に、その調整をタイマーにより制御し、イオン交換塔に
酸根を含むホウ素溶離液を通液させて酸根を除去する際
は、イオン交換塔出口のｐＨが７〜１に低下する時点を
検知して、この検知信号に基づいて通液停止を制御し、
ついで、通液停止後に水洗、及びアルカリ処理によりイ
オン交換塔内に充填したイオン交換樹脂をＯＨ型に調整
する際に、その調整を積算流量により制御する請求項２
または３に記載のホウ素溶離液の精製方法。4. When the packed ion exchange column is dewatered, the adjustment is controlled by a timer, and when the boron eluent containing the acid radical is passed through the ion exchange column to remove the acid radical, ion exchange is performed. Detecting the point in time when the pH at the outlet of the tower drops to 7 to 1 and controlling the stoppage of the flow based on this detection signal,
Then, when adjusting the ion exchange resin filled in the ion exchange tower to the OH type by washing with water and alkali treatment after stopping the flow, the adjustment is controlled by an integrated flow rate.
Or the method for purifying a boron eluate according to item 3.
法で得られた高純度のホウ酸溶液を濃縮、結晶化してホ
ウ酸固体とすることを特徴とするホウ素原料の製造方
法。5. A method for producing a boron raw material, comprising concentrating and crystallizing a high-purity boric acid solution obtained by the purification method according to claim 2 into a boric acid solid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2053633A1 (en) | 2001-10-19 | 2009-04-29 | Fujitsu Microelectronics Limited | Semiconductor substrate jig and method of manufacturing a semiconductor device |
| JPWO2014064754A1 (en) * | 2012-10-22 | 2016-09-05 | オルガノ株式会社 | Desalination method for boron-containing solution |
-
2000
- 2000-05-11 JP JP2000138547A patent/JP3883781B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2053633A1 (en) | 2001-10-19 | 2009-04-29 | Fujitsu Microelectronics Limited | Semiconductor substrate jig and method of manufacturing a semiconductor device |
| EP2058850A2 (en) | 2001-10-19 | 2009-05-13 | Fujitsu Microelectronics Limited | Semiconductor substrate jig and method of manufacturing a semiconductor device |
| JPWO2014064754A1 (en) * | 2012-10-22 | 2016-09-05 | オルガノ株式会社 | Desalination method for boron-containing solution |
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| Publication number | Publication date |
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| JP3883781B2 (en) | 2007-02-21 |
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