JP2003053342A - Method and device for removing impurity in boron- containing solution - Google Patents
Method and device for removing impurity in boron- containing solutionInfo
- Publication number
- JP2003053342A JP2003053342A JP2001244078A JP2001244078A JP2003053342A JP 2003053342 A JP2003053342 A JP 2003053342A JP 2001244078 A JP2001244078 A JP 2001244078A JP 2001244078 A JP2001244078 A JP 2001244078A JP 2003053342 A JP2003053342 A JP 2003053342A
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- Prior art keywords
- type
- boron
- exchange resin
- adjusted
- anion 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、Ｎａ、Ｃａの如き
陽イオンと、Ｃｌ、ＳＯ４の如き陰イオンと、不溶解物
を含むホウ素含有溶液を処理して高純度のホウ素含有水
を回収する方法及びそのための処理装置に関する。TECHNICAL FIELD The present invention relates to a treatment of a boron-containing solution containing a cation such as Na and Ca, an anion such as Cl and SO 4 , and an insoluble matter to recover highly pure boron-containing water. And a processing apparatus therefor.
【０００２】[0002]
【従来の技術】一般にニッケルメッキ液あるいはアルミ
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、これらを扱う工場で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、電解コンデンサー用
アルミ電極箔の化成処理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。さらにごみ焼却
場、石炭火力発電所等においてもホウ素を含む排水が発
生する。2. Description of the Related Art Generally, a nickel plating solution or an aluminum surface treatment solution contains a boron compound (boric acid, etc.), and a cleaning waste water containing boron is generated in a factory handling these compounds. In addition, factory wastewater containing boron is also generated in a factory that uses boron such as chemical conversion treatment of glass, glaze, and aluminum electrode foil for electrolytic capacitors. Furthermore, wastewater containing boron is also generated in refuse incineration plants, coal-fired power plants, and the like.
【０００３】ホウ素は植物にとっては必須微量元素であ
り、海水には４〜５ｍｇ／ｌ（リットル）程度含まれて
いることは周知のことである。一方、ホウ素はある濃度
以上に存在すると、植物の成長を阻害したり、動物に対
して神経障害を起こすおそれがあるといわれている。さ
らに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ｌｍｇ／ｌ以下が告示され、排水
基準も定められたため、これらのホウ素を含む工場排水
中のホウ素除去処理が必要となってきている。Boron is an essential trace element for plants, and it is well known that seawater contains about 4 to 5 mg / l (liter). On the other hand, it is said that when boron is present in a certain concentration or more, it may inhibit the growth of plants or cause nerve damage to animals. Furthermore, although the effects on the human body are not always clear, it has been pointed out that continued ingestion of low concentrations may cause health problems such as reduced reproductive function. In February 1999, lmg / l or less was announced as an environmental standard for boron, and wastewater standards were also set. Therefore, it is necessary to remove boron from factory wastewater containing these boron.
【０００４】したがって、ホウ素を含む工場排水からホ
ウ素を効率よく除去するとともに除去されたホウ素をホ
ウ酸等の再利用できる形に再生する技術の確立が望まれ
ている。そのための手段として、ホウ素を含有する排水
を陰イオン交換樹脂、あるいはホウ素選択吸着樹脂に吸
着させ、それにより排水を浄化する（特開平２−３２９
５２号公報、その他）とともに、樹脂に吸着したホウ素
を酸やアルカリを用いて溶離し、溶離液から陰イオンで
ある酸根やアルカリを除いて純度の高いホウ素含有水を
得る方法が知られている。Therefore, it has been desired to establish a technique for efficiently removing boron from wastewater containing boron and regenerating the removed boron into a reusable form such as boric acid. As a means for this, wastewater containing boron is adsorbed on an anion exchange resin or a boron selective adsorption resin to purify the wastewater (JP-A-2-329).
52, etc.), there is known a method in which boron adsorbed on a resin is eluted with an acid or an alkali to remove anionic acid radicals or alkalis from the eluent to obtain highly pure boron-containing water. .
【０００５】[0005]
【発明が解決しようとする課題】しかし、ホウ素を使用
する工場の中には、例えば電解コンデンサー用アルミ電
極箔の化成処理液のようにホウ素が数ｇ／ｌ含まれてお
り、化成処理を行うことにより当該溶液には、Ｎａ、Ｃ
ａの如き陽イオン、Ｃｌ、ＳＯ４如き陰イオン、更には
不溶解物が増加するため、更新することが必要となる。
この際更新された液のホウ素濃度は当然数ｇ／ｌと高い
ため、排水処理に加えるとホウ素濃度が高くなり、イオ
ン交換樹脂でホウ素除去を行うためには大量のイオン交
換樹脂を必要とする。However, some factories that use boron contain a few g / l of boron, such as the chemical conversion treatment liquid for aluminum electrode foils for electrolytic capacitors, so that chemical conversion treatment is performed. As a result, the solution contains Na, C
Since cations such as a, anions such as Cl and SO 4 , and insoluble matters increase, it is necessary to renew.
At this time, the renewed liquid has a high boron concentration of several g / l, so when added to the wastewater treatment, the boron concentration becomes high, and a large amount of ion exchange resin is required to remove boron with the ion exchange resin. .
【０００６】本発明はこうした事情を考慮してなされた
もので、Ｎａ、Ｃａの如き陽イオン、Ｃｌ、ＳＯ４の如
き陰イオン、更には不溶解物を含むホウ素濃度の高いホ
ウ素含有水を処理してホウ素含有水として再び工程で使
用する、或いは高純度のホウ酸として回収するホウ素含
有液の不純物除去方法及び装置を提供することを目的と
する。The present invention has been made in view of these circumstances, and treats cations such as Na and Ca, anions such as Cl and SO 4 , and boron-containing water having a high boron concentration containing insolubles. It is an object of the present invention to provide a method and an apparatus for removing impurities from a boron-containing liquid, which is used as boron-containing water again in the process or is recovered as high-purity boric acid.
【０００７】[0007]
【課題を解決するための手段】第１の発明に係るホウ素
含有液の不純物除去方法は、陽イオン、陰イオン、及び
不溶解物を含むホウ素含有溶液を、まずろ過機で不溶解
物を除去した後、Ｈ型に調整した強酸性陽イオン交換樹
脂を充填した陽イオン交換塔に通液することを特徴とす
る（請求項１記載）。A method for removing impurities from a boron-containing liquid according to a first aspect of the present invention comprises first removing a boron-containing solution containing cations, anions and insolubles with a filter. After that, the solution is passed through a cation exchange column filled with a strongly acidic cation exchange resin adjusted to H type (claim 1).
【０００８】第１の発明において、陽イオン交換塔に通
液した後、ＯＨ型に調整したＩ型若しくはII型強塩基性
陰イオン交換樹脂又は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に通液すること、
更にＨ型に調整した強酸性陽イオン交換樹脂及び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
又はＯＨ型に調整した弱塩基性陰イオン交換樹脂を混合
して充填した混床イオン交換塔に通液ことが好適であ
る。In the first invention, after passing through a cation exchange column, a type I or type II strong basic anion exchange resin adjusted to an OH type or a weak basic anion exchange resin adjusted to an OH type is used. Passing through the filled anion exchange tower,
Furthermore, a mixture of a strongly acidic cation exchange resin adjusted to H type and an I type or II type strongly basic anion exchange resin adjusted to OH type or a weak basic anion exchange resin adjusted to OH type is mixed and filled. It is preferable to pass the solution through a bed ion exchange column.
【０００９】第２の発明に係るホウ素含有液の不純物除
去方法は、陽イオン、陰イオン、及び不溶解物を含むホ
ウ素含有溶液を、まずろ過機で不溶解物を除去した後、
ＯＨ型に調整したＩ型若しくはII型強塩基性陰イオン交
換樹脂又は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に通液することを特徴とする
（請求項２記載）。A method for removing impurities from a boron-containing liquid according to a second aspect of the present invention is to remove a boron-containing solution containing a cation, an anion and an insoluble matter by first removing the insoluble matter with a filter,
The liquid is passed through an anion exchange column filled with an OH type I or II type strongly basic anion exchange resin or an OH type weakly basic anion exchange resin (claim 2). Description).
【００１０】第３の発明に係るホウ素含有液の不純物除
去方法は、陽イオン、陰イオン、及び不溶解物を含むホ
ウ素含有溶液を、まずろ過機で不溶解物を除去した後、
Ｈ型に調整した強酸性陽イオン交換樹脂及び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又は
ＯＨ型に調整した弱塩基性陰イオン交換樹脂を混合して
充填した混床イオン交換塔に通液することを特徴とする
（請求項５記載）。A method of removing impurities from a boron-containing liquid according to a third aspect of the present invention is to remove a boron-containing solution containing a cation, an anion and an insoluble matter by first removing the insoluble matter with a filter,
Mixed bed filled by mixing strongly acidic cation exchange resin adjusted to H type and I type or II type strong basic anion exchange resin adjusted to OH type or weak basic anion exchange resin adjusted to OH type The liquid is passed through the ion exchange tower (claim 5).
【００１１】本発明に係るホウ素含有液の不純物除去方
法において、前記混床イオン交換塔は複数直列に接続し
て通液し、上流側の混床イオン交換塔が飽和した際、こ
れを取り外して下流側の混床イオン交換塔を上流側に
し、下流側にあらたに前記混床イオン交換塔と同じ構成
の別な混床イオン交換塔を接続して通液することが好ま
しい。In the method for removing impurities from a boron-containing liquid according to the present invention, a plurality of the mixed bed ion exchange columns are connected in series to pass liquid, and when the mixed bed ion exchange column on the upstream side is saturated, it is removed. It is preferable that the mixed bed ion exchange column on the downstream side is set to the upstream side, and another mixed bed ion exchange column having the same structure as the mixed bed ion exchange column is newly connected to the downstream side for liquid passage.
【００１２】第４の発明に係るホウ素含有溶液の処理装
置は、陽イオン、陰イオン、及び不溶解物を含むホウ素
含有溶液をろ過するろ過機と、このろ過機の下流側に配
置された、Ｈ型に調整した強酸性陽イオン交換樹脂を充
填した陽イオン交換塔とを具備することを特徴とする
（請求項７記載）。A boron-containing solution treating apparatus according to a fourth aspect of the present invention comprises a filter for filtering a boron-containing solution containing cations, anions, and insoluble matters, and a filter disposed downstream of the filter. It is provided with a cation exchange column filled with a strongly acidic cation exchange resin adjusted to H type (claim 7).
【００１３】第４の発明において、陽イオン交換塔の後
段にさらにＯＨ型に調整したＩ型若しくはII型強塩基性
陰イオン交換樹脂又は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を、更にＨ型に調
整した強酸性陽イオン交換樹脂及び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又はＯＨ型に
調整した弱塩基性陰イオン交換樹脂を混合して充填した
混床イオン交換塔を配設することが望ましい。In the fourth aspect of the present invention, the cation exchange column is further provided with a type I or type II strong basic anion exchange resin adjusted to the OH type or a weak basic anion exchange resin adjusted to the OH type in the subsequent stage. The anion exchange column was further adjusted to a strongly acidic cation exchange resin adjusted to H type and I adjusted to OH type.
It is desirable to dispose a mixed bed ion exchange column in which a type II or type II strong basic anion exchange resin or a weak basic anion exchange resin adjusted to the OH type is mixed and packed.
【００１４】第５の発明に係るホウ素含有溶液の処理装
置は、陽イオン、陰イオン、及び不溶解物を含むホウ素
含有溶液をろ過するろ過機と、このろ過機の下流側に配
置された、ＯＨ型に調整したＩ型若しくはII型強塩基性
陰イオン交換樹脂又は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とを具備すること
を特徴とする（請求項８記載）。A boron-containing solution treating apparatus according to a fifth aspect of the present invention comprises a filter for filtering a boron-containing solution containing cations, anions, and insoluble matters, and a filter disposed downstream of the filter. An anion exchange column packed with an I-type or II-type strongly basic anion exchange resin adjusted to the OH type or a weakly basic anion exchange resin adjusted to the OH type. Description).
【００１５】第６の発明に係るホウ素含有溶液の処理装
置は、陽イオン、陰イオン、及び不溶解物を含むホウ素
含有溶液をろ過するろ過機と、このろ過機の下流側に配
置された、Ｈ型に調整した強酸性陽イオン交換樹脂及び
ＯＨ型に調整したＩ型若しくはII型強塩基性陰イオン交
換樹脂又はＯＨ型に調整した弱塩基性陰イオン交換樹脂
を混合して充填した混床イオン交換塔樹脂を混合して充
填した混床イオン交換塔とを具備することを特徴とする
（請求項１１記載）。A treatment apparatus for a boron-containing solution according to a sixth aspect of the present invention is a filter for filtering a boron-containing solution containing cations, anions and insoluble matters, and a filter disposed downstream of the filter. Mixed bed filled by mixing strongly acidic cation exchange resin adjusted to H type and I type or II type strong basic anion exchange resin adjusted to OH type or weak basic anion exchange resin adjusted to OH type And a mixed bed ion exchange column filled with a mixture of ion exchange column resins (claim 11).
【００１６】本発明に係るホウ素含有溶液の処理装置に
おいて、前記混床イオン交換塔は複数直列に接続して配
置するのが好ましい。In the apparatus for treating a boron-containing solution according to the present invention, it is preferable that a plurality of the mixed bed ion exchange columns are connected and arranged in series.
【００１７】[0017]
【発明の実施の形態】以下、本発明の実施形態を具体的
に説明する。本発明で処理の対象となる処理液は、Ｎ
ａ、Ｃａの如き陽イオン、或いはＣｌ、ＳＯ４の如き陰
イオン、更に不溶解物を含むホウ素含有溶液であり、こ
れには、電解コンデンサー用アルミ電極箔の化成処理液
に限らず、ホウ素を数ｇ／Ｌ程度含有し不純物を含んだ
ホウ素含有溶液を広く処理対象とすることができる。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be specifically described below. The treatment liquid to be treated in the present invention is N
a, a cation such as Ca, or an anion such as Cl or SO 4 , and a boron-containing solution containing an insoluble matter, which is not limited to the chemical conversion treatment solution for the aluminum electrode foil for electrolytic capacitors, A boron-containing solution containing impurities of about several g / L can be widely treated.
【００１８】この溶液は、例えばＢを数ｇ／ｌの他にＮ
ａ、Ｃａ等の陽イオン、ＳＯ4、Ｃｌ、等の陰イオン、
更には不溶解物を含んでいるが、後に示すように本発明
では、これらＮａ、Ｃａ、Ｍｇ等の陽イオン不純物、Ｓ
Ｏ４、Ｃｌ等の陰イオン不純物も効果的に除去される。This solution contains, for example, several g / l of B and N of
a, Ca, etc. cations, SO 4 , Cl, etc. anions,
Further, although it contains insoluble matter, in the present invention, as will be shown later, these cationic impurities such as Na, Ca and Mg, and S
Anionic impurities such as O 4 and Cl are also effectively removed.
【００１９】下記表１は、更新された電解コンデンサー
用アルミ電極箔化成処理液の組成の一例である。Table 1 below shows an example of the composition of the updated aluminum electrode foil chemical conversion treatment liquid for electrolytic capacitors.
【００２０】[0020]
【表１】 [Table 1]
【００２１】このようなホウ素以外の不純物を含む溶液
は、まずろ過機によって不溶解物を除去した後、Ｈ型に
調整した強酸性陽イオン交換樹脂を充填した陽イオン交
換塔に通液する。これによりＮａ、Ｃａ等の陽イオンが
除去される。続いて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又は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に通液す
る。これにより、ＳＯ ４、Ｃｌ等の陰イオンが除去され
る。出口液のｐＨは当該イオン交換塔が飽和に達するま
では中性であり、ホウ素はＨ３ＢＯ３分子として溶解し
ており漏出する。Solution containing impurities other than boron
First, remove insoluble matter with a filter, and then convert to H-type.
Cation exchange packed with prepared strong acid cation exchange resin
Pass through the exchange tower. As a result, cations such as Na and Ca
To be removed. Then I type or II type adjusted to OH type
Strongly basic anion exchange resin or weak base adjusted to OH type
Through an anion exchange column packed with a water-soluble anion exchange resin
It This allows SO Four, Cl and other anions are removed
It The pH of the outlet liquid is adjusted until the ion exchange tower reaches saturation.
Is neutral and boron is HThreeBOThreeDissolved as a molecule
And leak.
【００２２】このようにしてＮａ、Ｃａ等の陽イオン及
びＳＯ３、Ｃｌ等の陰イオンが除去されるが、上記の操
作に当たり、陽イオン交換塔に充填した陽イオン交換樹
脂、あるいは陰イオン交換塔に充填した陰イオン交換樹
脂が飽和したときには、処理液中の成分であるホウ素以
外の陽イオンや陰イオンが漏出する懸念がある。また、
陰イオン交換樹脂の再生に使用したＮａＯＨ中のＮａが
洗浄後にも僅かながら残留し、これがホウ素溶液中に混
入することもありうる。このような問題に対処するた
め、上記操作を終えた後、混床イオン交換塔に通液する
のが効果的である。陰イオン交換塔より除去されるべき
イオンが漏出するとｐＨ、あるいは電気伝導率の急激な
変化が生ずるため、陰イオン交換塔の出口配管にｐＨ計
あるいは電気伝導度計を設置することにより通水の終点
管理が容易になる。In this way, cations such as Na and Ca and anions such as SO 3 and Cl are removed. In the above operation, the cation exchange resin packed in the cation exchange column or the anion exchange resin is removed. When the anion exchange resin packed in the tower is saturated, there is a concern that cations and anions other than boron, which is a component in the treatment liquid, may leak out. Also,
It is possible that Na in the NaOH used for regeneration of the anion exchange resin remains slightly after the washing, which may be mixed in the boron solution. In order to deal with such a problem, it is effective to pass the solution through the mixed bed ion exchange column after the above operation is completed. Leakage of ions to be removed from the anion exchange tower causes a sudden change in pH or electric conductivity. Therefore, install a pH meter or electric conductivity meter in the outlet pipe of the anion exchange tower to pass water. End point management becomes easy.
【００２３】この混床イオン交換塔には、（１）Ｈ型に
調整した強酸性陽イオン交換樹脂及び（２）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又は
ＯＨ型に調整した弱塩基性陰イオン交換樹脂の２つのタ
イプの樹脂が混合して充填されており、この混床イオン
塔に通液することにより上記汚染物質（陽イオン及び陰
イオン）が完全に除去され、極めて純度の高いホウ素溶
液を得ることができる。なお、混床イオン交換塔におけ
るＨ型に調整した強酸性陽イオン交換樹脂とＯＨ型に調
整した陰イオン交換樹脂（Ｉ型若しくはII型強塩基性陰
イオン交換樹脂あるいはＯＨ型に調整した弱塩基性陰イ
オン交換樹脂）の混合比率は、混合のしやすさを考慮し
て１：１とするのがよい。In this mixed bed ion exchange column, (1) a strongly acidic cation exchange resin adjusted to H type and (2) a type I or II type strongly basic anion exchange resin or OH type adjusted to OH type. The two types of weakly basic anion-exchange resin prepared as above are mixed and packed, and the contaminants (cation and anion) are completely removed by passing through this mixed bed ion tower. As a result, an extremely pure boron solution can be obtained. The strong acid cation exchange resin adjusted to H type and the anion exchange resin adjusted to OH type in the mixed bed ion exchange column (type I or type II strong basic anion exchange resin or weak base adjusted to OH type). The mixing ratio of the (cationic anion exchange resin) is preferably 1: 1 in consideration of easiness of mixing.
【００２４】上記の構成により、極めて高純度のホウ素
溶液を安定して得ることができるが、実際の操業上の問
題としては、混床イオン交換塔の終点管理を誤って陽イ
オンあるいは陰イオンが漏出する危険性がある。本発明
では、そのための対策として、混床イオン交換塔として
同型のものを２基以上用意し、これらを直列に接続した
ものとする。これにより、直列に接続した混床イオン交
換塔のうち先頭の混床イオン交換塔から陽イオンあるい
は陰イオンが漏出しても、それは、後続の同型のイオン
交換塔により除去される。これにより、最終の混床イオ
ン交換塔からいずれのイオンも漏出することはない。更
には陽イオン交換塔、陰イオン交換塔の代わりに混床イ
オン交換塔を複数接続することも好適である。With the above-mentioned constitution, an extremely high-purity boron solution can be stably obtained, but as a practical problem, cations or anions are erroneously managed by mistakenly controlling the end point of the mixed bed ion exchange column. There is a risk of leakage. In the present invention, as a countermeasure therefor, two or more mixed bed ion exchange towers of the same type are prepared, and these are connected in series. As a result, even if cations or anions leak out from the leading mixed bed ion exchange column of the mixed bed ion exchange columns connected in series, they will be removed by the subsequent ion exchange column of the same type. As a result, none of the ions leak from the final mixed bed ion exchange column. Further, it is also preferable to connect a plurality of mixed bed ion exchange towers instead of the cation exchange tower and the anion exchange tower.
【００２５】このような同型のイオン交換塔を直列に接
続してなる一群のイオン交換塔の管理は、いわゆる順送
り交換方式により行うことができる。この順送り交換方
式とは、複数の同型のイオン交換塔を直列に接続して操
業している場合に、先頭側のイオン交換塔から除去され
るべきイオン種が漏出し始めたとき、操業を一旦中断
し、先頭側イオン交換塔を取り外し、その後に後続イオ
ン交換塔を当てはめ、後続イオン交換塔の後には新しく
調整されたイオン交換塔を設置する方式をいう。この方
式を採用することにより、イオン交換塔の能力を完全に
使いきることができ、経済的な操業が可能になる。ま
た、先頭側のイオン交換塔から除去されるべきイオンが
漏出するとｐＨ、あるいは電気伝導率の急激な変化が生
ずるため、先頭側の出口配管にｐＨ計あるいは電気伝導
度計を設置することにより通水の終点管理が容易にな
る。Management of a group of ion exchange towers in which the same type of ion exchange towers are connected in series can be performed by a so-called progressive exchange method. This sequential feed exchange system is a system in which a plurality of ion exchange towers of the same type are connected in series, and when the ion species to be removed from the ion exchange tower on the leading side start to leak, the operation is temporarily stopped. It is a system in which the ion exchange column on the leading side is removed, the subsequent ion exchange column is applied after the suspension, and a newly adjusted ion exchange column is installed after the subsequent ion exchange column. By adopting this method, the capacity of the ion exchange column can be completely used up, and economical operation becomes possible. Also, if ions to be removed from the ion exchange tower on the front side leak out, a sharp change in pH or electric conductivity occurs. Therefore, by installing a pH meter or electric conductivity meter in the outlet pipe on the front side, Water end point management becomes easy.
【００２６】なお、これらの操作は得られるホウ素含有
溶液を工程で使用する場合の必要な不純物の水準によっ
て好適な手段を選択することが出来る。更に、ここで得
られたホウ素溶離液を濃縮・結晶化等によりホウ酸とす
れば例えばフェロボロンの原料として使用することも可
能である。For these operations, suitable means can be selected according to the level of impurities required when the obtained boron-containing solution is used in the process. Furthermore, if the boron eluate obtained here is converted to boric acid by concentration and crystallization, it can be used, for example, as a raw material for ferroboron.
【００２７】本発明の実施に適するプラントの構成の代
表的な例を図１、図２、図３、図４、図５に示した。図
１は、ホウ素含有溶液の流入順に、ろ過機１、Ｈ型に調
整した強酸性陽イオン交換樹脂を充填した陽イオン交換
塔２を配設した構成となっている。図２は、ホウ素含有
溶液の流入順に、ろ過機１、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又は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
３を配設した構成となっている。Representative examples of plant configurations suitable for carrying out the present invention are shown in FIGS. 1, 2, 3, 4, and 5. FIG. 1 shows a configuration in which a filter 1 and a cation exchange column 2 filled with a strongly acidic cation exchange resin adjusted to an H type are arranged in the order of inflow of a boron-containing solution. FIG. 2 shows, in the order of inflow of a boron-containing solution, a filter 1 and an anion filled with an OH type I or II type strongly basic anion exchange resin or an OH type weakly basic anion exchange resin. The exchange tower 3 is arranged.
【００２８】図３は、ホウ素含有溶液の流入順に、ろ過
機１、Ｈ型に調整した強酸性陽イオン交換樹脂を充填し
た陽イオン交換塔２、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又は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３を配
設した構成となっている。これにより本発明の基本的な
目的が達成される。なお、図３の構成では、陰イオン交
換塔３の出口配管にＰＨ計あるいは電気伝導度計を設置
することにより、終点を求めることができる。FIG. 3 shows, in the order of inflow of the boron-containing solution, a filter 1, a cation exchange column 2 filled with a strongly acidic cation exchange resin adjusted to H type, and an I type or II type adjusted to OH type.
The configuration is such that an anion exchange column 3 filled with a strong base anion exchange resin or a weakly basic anion exchange resin adjusted to the OH type is arranged. This achieves the basic object of the invention. In the configuration of FIG. 3, the end point can be obtained by installing a PH meter or an electric conductivity meter in the outlet pipe of the anion exchange tower 3.
【００２９】図４は、ホウ素含有溶液の流入順に、ろ過
機１、Ｈ型に調整した強酸性陽イオン交換樹脂及び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
脂又はＯＨ型に調整した弱塩基性陰イオン交換樹脂を混
合して充填した混床塔４を配設した構成となっている。
なお、図４の構成では、混床塔４の出口配管にｐＨ計あ
るいは電気伝導度計を配置することにより、終点を求め
ることができる。FIG. 4 shows a filter 1, a strongly acidic cation exchange resin adjusted to H type and OH in the order of inflow of the boron-containing solution.
A type I or II type strong basic anion exchange resin adjusted to a mold or a weak basic anion exchange resin adjusted to an OH type is mixed and packed in the mixed bed column 4.
In the configuration of FIG. 4, the end point can be obtained by disposing a pH meter or an electric conductivity meter in the outlet pipe of the mixed bed tower 4.
【００３０】更に、図５は、ホウ素含有溶液の流入順
に、ろ過機１、Ｈ型に調整した強酸性陽イオン交換樹脂
を充填した陽イオン交換塔２、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又は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３、Ｈ型に調整した強酸性陽イオン交換樹脂及び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
脂又はＯＨ型に調整した弱塩基性陰イオン交換樹脂を混
合して充填した混床塔４を配設した構成となっている。
これにより高純度のホウ素含有液を得ることができる。
なお、図５の構成では、陰イオン交換塔３あるいは混床
塔４の出口配管のいずれか、又は双方にｐＨ計あるいは
電気伝導度計を配置することにより、終点を求めること
ができる。Further, FIG. 5 shows, in the order of inflow of the boron-containing solution, a filter 1, a cation exchange column 2 filled with a strongly acidic cation exchange resin adjusted to H type, and an I type or II type adjusted to OH type. Anion exchange column 3 packed with a strongly basic anion exchange resin or a weakly basic anion exchange resin adjusted to OH type, a strongly acidic cation exchange resin and OH adjusted to H type
A type I or II type strong basic anion exchange resin adjusted to a mold or a weak basic anion exchange resin adjusted to an OH type is mixed and packed in the mixed bed column 4.
Thereby, a high-purity boron-containing liquid can be obtained.
In the configuration of FIG. 5, the end point can be obtained by disposing a pH meter or an electric conductivity meter in either or both of the outlet pipes of the anion exchange tower 3 or the mixed bed tower 4.
【００３１】[0031]
【実施例】内径１４ｍｍ、高さ５２５ｍｍのアクリル製
カラムを２本準備した。そのうち１本目にはＨ型に調整
した強酸性陽イオン交換樹脂１０ｍＬを充填して陽イオ
ン交換塔とした。他の２本目にはＯＨ型に調整した弱塩
基性陰イオン交換樹脂１０ｍＬを充填して陰イオン交換
塔とした。[Example] Two acrylic columns having an inner diameter of 14 mm and a height of 525 mm were prepared. The first column was filled with 10 mL of a strongly acidic cation exchange resin adjusted to H type to form a cation exchange column. The other second column was filled with 10 mL of a weakly basic anion exchange resin adjusted to the OH type to form an anion exchange column.
【００３２】作成した装置にイオン交換水を流速１００
ｍＬ／ｈでｌｈ通液してイオン交換樹脂に残存する薬剤
を抽出、洗浄した後、圧縮空気により脱水状態にし、そ
の後、上記表１に示すホウ素含有液を、ＳＳを除去した
後に流速１００ｍＬ／ｈで通液した。A flow rate of ion-exchanged water of 100 was applied to the prepared apparatus.
After passing through 1 h at mL / h to extract and wash the drug remaining in the ion exchange resin, it is dehydrated by compressed air, and then the boron-containing liquid shown in Table 1 above is removed at a flow rate of 100 mL / The solution was passed at h.
【００３３】図６は、陰イオン交換塔の出口側における
処理水のＢ、Ｎａ、ＰＨ及び電気伝導度と通液量（Ｂ
Ｖ）との関係図である。ここにおいて、７００ＢＶまで
はＮａイオンの漏出はなく、処理水は高純度のホウ素液
が得られた。またＣｌ、或いはＳＯ４の如き陰イオンが
漏出し始めると、ｐＨの急激な低下が、Ｎａ等の陽イオ
ンの漏出が始まるとｐＨの上昇が起こるため、容易に終
点を管理できる。更には電気伝導度の上昇によっても管
理できる。FIG. 6 shows B, Na, and PH of treated water at the outlet side of the anion exchange tower, and the electrical conductivity and the passing amount (B
It is a relationship diagram with V). Here, there was no leakage of Na ions up to 700 BV, and high-purity boron liquid was obtained as the treated water. Further, when an anion such as Cl or SO 4 begins to leak, a sharp drop in pH occurs, and when a cation such as Na begins to leak, the pH rises, so the end point can be easily controlled. Furthermore, it can be managed by increasing the electric conductivity.
【００３４】このようにして得られたホウ素液を通常の
方法で固形化すると、下記表２に示すような不純物組成
を持つホウ酸が得られる。これは当該工程でホウ素を再
利用することが出来ると同時に、ボロン系合金鉄の原料
としては勿論ガラス、釉薬等の原料として使用すること
ができる。When the boron solution thus obtained is solidified by a usual method, boric acid having an impurity composition as shown in Table 2 below is obtained. In this process, boron can be reused in the process, and at the same time, it can be used as a raw material for boron-based ferroalloys as well as a raw material for glass, glaze, and the like.
【００３５】[0035]
【表２】 [Table 2]
【００３６】[0036]
【発明の効果】以上詳記したように本発明によれば、Ｎ
ａ、Ｃａの如き陽イオン、Ｃｌ、ＳＯ ４の如き陰イオ
ン、更には不溶解物を含むホウ素濃度の高いホウ素含有
水を処理してホウ素含有水として再び工程で使用する、
或いは高純度のホウ素として回収するホウ素含有液の不
純物除去方法及び装置を提供できる。As described above in detail, according to the present invention, N
a, cation such as Ca, Cl, SO FourYin Io like
In addition, boron containing a high concentration of boron including insoluble matter
The water is treated and used again in the process as boron-containing water,
Alternatively, the boron-containing liquid recovered as high-purity boron is
A pure substance removing method and device can be provided.
【図１】本発明の一実施例に係るほう素含有液の不純物
除去装置の説明図。FIG. 1 is an explanatory diagram of an apparatus for removing impurities from a boron-containing liquid according to an embodiment of the present invention.
【図２】本発明の他の実施例に係るほう素含有液の不純
物除去装置の説明図。FIG. 2 is an explanatory diagram of an impurity removing apparatus for a boron-containing liquid according to another embodiment of the present invention.
【図３】本発明の他の実施例に係るほう素含有液の不純
物除去装置の説明図。FIG. 3 is an explanatory diagram of an impurity removing apparatus for a boron-containing liquid according to another embodiment of the present invention.
【図４】本発明の他の実施例に係るほう素含有液の不純
物除去装置の説明図。FIG. 4 is an explanatory diagram of an impurity removing apparatus for a boron-containing liquid according to another embodiment of the present invention.
【図５】本発明の他の実施例に係るほう素含有液の不純
物除去装置の説明図。FIG. 5 is an explanatory diagram of an impurity removing apparatus for a boron-containing liquid according to another embodiment of the present invention.
【図６】本発明の他の実施例に係るほう素含有液の不純
物除去装置の説明図。FIG. 6 is an explanatory diagram of an impurity removing apparatus for a boron-containing liquid according to another embodiment of the present invention.
１…ろ過機、 ２…陽イオン交換塔、 ３…陰イオン交換塔、 ４…混床イオン交換塔。 1 ... filter, 2 ... Cation exchange tower, 3 ... Anion exchange tower, 4 mixed bed ion exchange tower.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 木谷 仁紀 徳島県阿南市橘町幸野62番地１ 日本電工 株式会社研究所内 (72)発明者 古荘 三郎 東京都豊島区南大塚三丁目43番11号 日本 錬水株式会社内 Ｆターム(参考） 4D025 AA09 AB07 AB14 AB18 AB19 BA11 BA16 BB02 BB04 BB07 BB09 BB18 DA10 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Hitoki Kitani 62, Yukino, Tachibana-cho, Anan City, Tokushima Prefecture Nippon Electric Works Inside Institute (72) Inventor Saburo Furuso 33-13-1 Minami-Otsuka, Toshima-ku, Tokyo Japan Renshui Co., Ltd. F term (reference) 4D025 AA09 AB07 AB14 AB18 AB19 BA11 BA16 BB02 BB04 BB07 BB09 BB18 DA10
Claims (12)
むホウ素含有溶液を、まずろ過機で不溶解物を除去した
後、Ｈ型に調整した強酸性陽イオン交換樹脂を充填した
陽イオン交換塔に通液することを特徴とするホウ素含有
溶液の不純物除去方法。1. A boron-containing solution containing a cation, an anion, and an insoluble matter is first filtered to remove the insoluble matter, and then the cation is filled with a strongly acidic cation exchange resin adjusted to H type. A method for removing impurities from a boron-containing solution, which comprises passing the solution through an exchange column.
むホウ素含有溶液を、まずろ過機で不溶解物を除去した
後、ＯＨ型に調整したＩ型若しくはII型強塩基性陰イオ
ン交換樹脂又は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に通液することを特徴と
するホウ素含有溶液の不純物除去方法。2. A boron-containing solution containing a cation, an anion, and an insoluble matter is first filtered to remove the insoluble matter, and then the OH type is adjusted to a type I or type II strong basic anion exchange. A method for removing impurities from a boron-containing solution, which comprises passing the solution through an anion exchange column packed with a resin or an OH type weakly basic anion exchange resin.
前記陽イオン交換塔に通液した後、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又は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
交換塔に通液することを特徴とする請求項１に記載のホ
ウ素含有溶液の不純物除去方法。3. The insoluble matter is removed by the filter, then the solution is passed through the cation exchange column, and then the OH type is adjusted.
The type B or II type strong basic anion exchange resin or the weak basic anion exchange resin adjusted to OH type is passed through an anion exchange column filled with the boron-containing solution according to claim 1. Impurity removal method.
陽イオン交換塔、陰イオン交換塔に順次通液した後、Ｈ
型に調整した強酸性陽イオン交換樹脂及び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又はＯ
Ｈ型に調整した弱塩基性陰イオン交換樹脂を混合して充
填した混床イオン交換塔に通液することを特徴とする請
求項３に記載のホウ素含有溶液の不純物除去方法。4. The insoluble matter is removed by the filter, and then the solution is sequentially passed through a cation exchange column and an anion exchange column, and then H
-Type strong acid cation exchange resin and OH-type adjusted type I or type II strong basic anion exchange resin or O
The method for removing impurities from a boron-containing solution according to claim 3, wherein the solution is passed through a mixed bed ion exchange column in which a weakly basic anion exchange resin adjusted to H type is mixed and packed.
むホウ素含有溶液を、まずろ過機で不溶解物を除去した
後、Ｈ型に調整した強酸性陽イオン交換樹脂及び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
又はＯＨ型に調整した弱塩基性陰イオン交換樹脂を混合
して充填した混床イオン交換塔に通液することを特徴と
するホウ素含有溶液の不純物除去方法。5. A boron-containing solution containing a cation, an anion, and an insoluble matter is first removed by a filter to remove the insoluble matter, and then adjusted to an H-type strong acid cation exchange resin and an OH-type solution. Of a boron-containing solution characterized by being passed through a mixed bed ion exchange column filled with a mixture of the type I or type II strong basic anion exchange resin or the weak basic anion exchange resin adjusted to the OH type. Impurity removal method.
して通液し、上流側の混床イオン交換塔が飽和した際こ
れを取り外して下流側の混床イオン交換塔を上流側に
し、下流側にあらたに前記混床イオン交換塔と同じ構成
の別な混床イオン交換塔を接続して通液することを特徴
とする請求項４もしくは請求項５記載のほう素含有溶液
の不純物除去方法。6. A plurality of said mixed bed ion exchange towers are connected in series for liquid passage, and when the upstream mixed bed ion exchange tower is saturated, it is removed to make the downstream mixed bed ion exchange tower upstream. The impurity of the boron-containing solution according to claim 4 or 5, wherein another mixed bed ion exchange column having the same structure as the mixed bed ion exchange column is newly connected to the downstream side to pass the liquid. Removal method.
むホウ素含有溶液をろ過するろ過機と、このろ過機の下
流側に配置された、Ｈ型に調整した強酸性陽イオン交換
樹脂を充填した陽イオン交換塔とを具備することを特徴
とするホウ素含有溶液の処理装置。7. A filter for filtering a boron-containing solution containing a cation, an anion, and an insoluble matter, and a H-type adjusted strong acid cation exchange resin disposed downstream of the filter. An apparatus for treating a boron-containing solution, comprising a packed cation exchange column.
むホウ素含有溶液をろ過するろ過機と、このろ過機の下
流側に配置された、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又は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とを具備
することを特徴とするホウ素含有溶液の処理装置。8. A filter for filtering a boron-containing solution containing a cation, an anion, and an insoluble matter, and an I-type or II-type strong base adjusted to an OH type, which is arranged on the downstream side of the filter. And an anion exchange column filled with a weakly basic anion exchange resin adjusted to an OH type. 1. An apparatus for treating a boron-containing solution, comprising:
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
又は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を配設したことを特徴とする請求項
７に記載のホウ素含有溶液の処理装置。9. Anion filled with an OH type I or II type strongly basic anion exchange resin or an OH type weakly basic anion exchange resin on the downstream side of the cation exchange column. An apparatus for treating a boron-containing solution according to claim 7, wherein an exchange tower is provided.
に調整した強酸性陽イオン交換樹脂及び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又はＯＨ
型に調整した弱塩基性陰イオン交換樹脂を混合して充填
した混床イオン交換塔樹脂を混合して充填した混床イオ
ン交換塔を配設したことを特徴とする請求項９に記載の
ホウ素含有溶液の処理装置。10. A strongly acidic cation exchange resin adjusted to H type and a type I or type II strong basic anion exchange resin adjusted to OH type or OH on the downstream side of the anion exchange column.
The mixed bed ion exchange column filled with a mixed bed ion exchange column resin mixed with and filled with a weakly basic anion exchange resin adjusted to a mold is arranged. Equipment for containing solution.
含むホウ素含有溶液をろ過するろ過機と、このろ過機の
下流側に配置された、Ｈ型に調整した強酸性陽イオン交
換樹脂及びＯＨ型に調整したＩ型若しくはII型強塩基性
陰イオン交換樹脂又はＯＨ型に調整した弱塩基性陰イオ
ン交換樹脂を混合して充填した混床イオン交換塔樹脂を
混合して充填した混床イオン交換塔とを具備することを
特徴とするホウ素含有溶液の処理装置。11. A filter for filtering a boron-containing solution containing a cation, an anion, and an insoluble matter, a H-type adjusted strong acidic cation exchange resin disposed downstream of the filter, and Mixed bed filled by mixing OH type I or II type strong basic anion exchange resin or OH adjusted weak basic anion exchange resin and mixed and filled ion exchange tower resin An apparatus for treating a boron-containing solution, comprising an ion exchange tower.
置されていることを特徴とする請求項１０もしくは請求
項１１記載のホウ素含有溶液の処理装置。12. The apparatus for treating a boron-containing solution according to claim 10 or 11, wherein a plurality of the mixed bed ion exchange columns are arranged in series.
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| JP2001244078A JP2003053342A (en) | 2001-08-10 | 2001-08-10 | Method and device for removing impurity in boron- containing solution |
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| JP2001244078A JP2003053342A (en) | 2001-08-10 | 2001-08-10 | Method and device for removing impurity in boron- containing solution |
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|---|---|
| JP2003053342A true JP2003053342A (en) | 2003-02-25 |
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|---|---|---|---|
| JP2001244078A Pending JP2003053342A (en) | 2001-08-10 | 2001-08-10 | Method and device for removing impurity in boron- containing solution |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005351881A (en) * | 2004-05-13 | 2005-12-22 | National Institute Of Advanced Industrial & Technology | Coexistent anion treatment device and method |
| JP2009285610A (en) * | 2008-05-30 | 2009-12-10 | Kurita Water Ind Ltd | Method and apparatus for treating water-soluble resin component-containing alkaline wastewater |
| JP2010119978A (en) * | 2008-11-21 | 2010-06-03 | Kotobuki Kakoki Kk | Apparatus for treating wastewater |
| CN104736484A (en) * | 2012-10-22 | 2015-06-24 | 奥加诺株式会社 | Method of desalinating boron-containing solution |
| JP2016117523A (en) * | 2014-12-22 | 2016-06-30 | オルガノ株式会社 | Ion exchange resin filling method, ion exchange resin filling device, and ion exchange resin storage method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60225689A (en) * | 1984-04-23 | 1985-11-09 | Japan Organo Co Ltd | Treatment of waste boric acid solution |
| JP2002126541A (en) * | 2000-10-23 | 2002-05-08 | Nippon Denko Kk | Processing method of boron elute containing alkali |
-
2001
- 2001-08-10 JP JP2001244078A patent/JP2003053342A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60225689A (en) * | 1984-04-23 | 1985-11-09 | Japan Organo Co Ltd | Treatment of waste boric acid solution |
| JP2002126541A (en) * | 2000-10-23 | 2002-05-08 | Nippon Denko Kk | Processing method of boron elute containing alkali |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005351881A (en) * | 2004-05-13 | 2005-12-22 | National Institute Of Advanced Industrial & Technology | Coexistent anion treatment device and method |
| JP4665154B2 (en) * | 2004-05-13 | 2011-04-06 | 独立行政法人産業技術総合研究所 | Coexisting anion treatment apparatus and method |
| JP2009285610A (en) * | 2008-05-30 | 2009-12-10 | Kurita Water Ind Ltd | Method and apparatus for treating water-soluble resin component-containing alkaline wastewater |
| JP2010119978A (en) * | 2008-11-21 | 2010-06-03 | Kotobuki Kakoki Kk | Apparatus for treating wastewater |
| CN104736484A (en) * | 2012-10-22 | 2015-06-24 | 奥加诺株式会社 | Method of desalinating boron-containing solution |
| JPWO2014064754A1 (en) * | 2012-10-22 | 2016-09-05 | オルガノ株式会社 | Desalination method for boron-containing solution |
| JP2016117523A (en) * | 2014-12-22 | 2016-06-30 | オルガノ株式会社 | Ion exchange resin filling method, ion exchange resin filling device, and ion exchange resin storage method |
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