JP2001225081A - Method for removing boron in wastewater having high concentration of salts - Google Patents
Method for removing boron in wastewater having high concentration of saltsInfo
- Publication number
- JP2001225081A JP2001225081A JP2000036739A JP2000036739A JP2001225081A JP 2001225081 A JP2001225081 A JP 2001225081A JP 2000036739 A JP2000036739 A JP 2000036739A JP 2000036739 A JP2000036739 A JP 2000036739A JP 2001225081 A JP2001225081 A JP 2001225081A
- Authority
- JP
- Japan
- Prior art keywords
- wastewater
- boron
- salt concentration
- high salt
- magnesium
- 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.)
- Granted
Links
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- Physical Water Treatments (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、塩類濃度の高い排
水中のほう素除去方法に係り、特に表面処理工場や産業
廃棄物処分場などの有害物質を処理した後の塩類濃度の
高い排水、塩類濃度が高く炭酸塩、有機物を含む排水中
のほう素除去方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing boron from wastewater having a high salt concentration, and particularly to a wastewater having a high salt concentration after treating harmful substances such as a surface treatment plant or an industrial waste disposal site. The present invention relates to a method for removing boron in wastewater having a high salt concentration and containing carbonates and organic substances.
【０００２】[0002]
【従来の技術】従来、表面処理工場や産業廃棄物処分場
の排水中に含まれるほう素の除去は、排水中の他の有害
物質を処理した後、グルカミン形のイオン交換樹脂でほ
う素を選択的に吸着するキレート樹脂法で行われてい
る。また、めっき排水中に含まれるほう素については、
めっき排水中にニッケルイオン共存下でマグネシウムイ
オンを添加して、ほう素、マグネシウム及びニッケルの
不溶化物として共沈させるほう素の除去法を提案した
（特願平１１−２９９０２）。2. Description of the Related Art Conventionally, boron contained in wastewater from a surface treatment plant or an industrial waste disposal site is removed by treating other harmful substances in the wastewater and then removing the boron with a glucamine-type ion exchange resin. It is performed by a chelate resin method of selectively adsorbing. For boron contained in plating wastewater,
A method of removing boron by adding magnesium ions to the plating wastewater in the presence of nickel ions to coprecipitate as insolubilized boron, magnesium and nickel was proposed (Japanese Patent Application No. 11-29902).
【０００３】[0003]
【発明が解決しようとする課題】従来のキレート樹脂法
による排水中のほう素除去では、吸着量が少なくまた処
理能力も小さい。またキレート樹脂に飽和に吸着したほ
う素を溶離液で回収するが、回収したほう素溶液の処分
が困難であるという問題がある。さらに、キレート樹脂
は高価であり、大量の排水を処理するにはコストがかか
るという問題がある。また、先に提案した、めっき洗浄
排水中のほう素をニッケルイオン共存下でマグネシウム
イオンを添加して不溶化物として除去処理する方法で
は、溶存物質が少ない排水に対しては効果的にほう素を
除去することができ、コストも安価で有効である。しか
しながら、表面処理工場や産業廃棄物処分場等の総合排
水で有害物質を処理した後の塩類浪度の高い排水や、有
機物を生物処理した後の有機物及び炭駿塩が多い排水中
のほう素は、充分に除去することができなかった。In the removal of boron from waste water by the conventional chelating resin method, the amount of adsorption is small and the processing capacity is small. Further, the boron adsorbed to the chelate resin is recovered by the eluent, but there is a problem that it is difficult to dispose of the recovered boron solution. Further, there is a problem that the chelate resin is expensive, and it is costly to treat a large amount of wastewater. In addition, the previously proposed method of removing boron as insoluble material by adding magnesium ions in the presence of nickel ions in the plating washing wastewater effectively removes boron from wastewater with little dissolved material. It can be removed and the cost is low and effective. However, boron in wastewater with a high degree of salt waste after treating harmful substances with comprehensive wastewater from surface treatment plants and industrial waste disposal sites, and in wastewater that is rich in organic matter and charcoal salt after biological treatment of organic matter. Could not be sufficiently removed.
【０００４】[0004]
【課題を解決するための手段】本発明は、上記課題を解
決するためのもので、塩類濃度の高い排水中のほう素を
除去する方法において、前記排水にマグネシウムイオン
を含む溶液を添加し、次いで水酸化ナトリウム溶液を添
加してｐＨ１０．５〜１１．５に調節し、ほう素及びマ
グネシウムの不溶解物質を生成させ、前記不溶解物質を
分離することによりほう素を除去することを特徴とする
塩類濃度の高い排水中のほう素除去方法である。また、
本発明は、塩類濃度の高い排水中のほう素を除去する方
法において、排水が炭酸塩を含む場合には、前記排水の
ｐＨを２以下に保ち空気曝気または真空脱気して二酸化
炭素を除去する処理を行った後に、排水にマグネシウム
イオンを含む溶液を添加し、次いで水酸化ナトリウム溶
液を添加してｐＨ１０．５〜１１．５に調節し、ほう素
及びマグネシウムの不溶解物質を生成させ、前記不溶解
物質を分離することによりほう素を除去することを特徴
とする塩類濃度の高い排水中のほう素除去方法である。Means for Solving the Problems The present invention has been made to solve the above-mentioned problems. In a method for removing boron in wastewater having a high salt concentration, a solution containing magnesium ions is added to the wastewater. Then, a sodium hydroxide solution is added to adjust the pH to 10.5 to 11.5 to generate an insoluble substance of boron and magnesium, and the boron is removed by separating the insoluble substance. This is a method for removing boron from wastewater with a high salt concentration. Also,
The present invention relates to a method for removing boron in wastewater having a high salt concentration, wherein when the wastewater contains carbonate, the pH of the wastewater is kept at 2 or less to remove carbon dioxide by air aeration or vacuum degassing. After performing the treatment, a solution containing magnesium ions is added to the waste water, and then a sodium hydroxide solution is added to adjust the pH to 10.5-11.5, thereby producing an insoluble substance of boron and magnesium, A method for removing boron from wastewater having a high salt concentration, wherein boron is removed by separating the insoluble substance.
【０００５】また、本発明は、塩類濃度の高い排水中の
ほう素を除去する方法において、排水が炭酸塩及び有機
物を含む場合には、前記排水のｐＨを２以下に保ち空気
曝気または真空脱気して二酸化炭素を除去する処理を行
った後に、排水にマグネシウムイオンを含む溶液と２価
の鉄イオンを含む溶液を添加し、次いで水酸化ナトリウ
ム溶液を添加してｐＨ１０．５〜１１．５に調節し、ほ
う素及びマグネシウムの不溶解物質を生成させ、前記不
溶解物質を分離することによりほう素を除去することを
特徴とする塩類濃度の高い排水中のほう素除去方法であ
る。また、本発明は、塩類濃度の高い排水が炭酸塩及び
有機物を含む場合であって排水に含まれる有機物の全炭
素量が３００ｍｇ／Ｌ以上の場合には、２価の鉄イオン
を含む溶液の添加量が、１００ｍｇ／Ｌ〜５００ｍｇ／
Ｌであることを特徴とするものである。また２価の鉄イ
オンは、塩化鉄溶液であることを特徴とするものであ
る。また、本発明は、塩類濃度の高い排水中のほう素を
除去する方法において、排水が炭酸塩及び有機物を含む
場合には、前記排水のｐＨを２以下に保ち空気曝気また
は真空脱気して二酸化炭素を除去する処理、活性炭吸着
処理して有機物の除去を行った後に、排水にマグネシウ
ムイオンを含む溶液を添加し、次いで水酸化ナトリウム
溶液を添加してｐＨ１０．５〜１１．５に調節し、ほう
素及びマグネシウムの不溶解物質を生成させ、前記不溶
解物質を分離することによりほう素を除去することを特
徴とする塩類濃度の高い排水中のほう素除去方法であ
る。Further, the present invention provides a method for removing boron in wastewater having a high salt concentration, wherein when the wastewater contains carbonates and organic substances, the pH of the wastewater is kept at 2 or less and air aeration or vacuum degassing is performed. After performing a treatment for removing carbon dioxide by taking care, a solution containing magnesium ions and a solution containing divalent iron ions are added to the waste water, and then a sodium hydroxide solution is added to adjust the pH to a pH of 10.5 to 11.5. , A boron and magnesium insoluble material is produced, and boron is removed by separating the insoluble material to remove boron. Further, the present invention relates to a case where the wastewater having a high salt concentration contains carbonates and organic substances, and the total carbon content of the organic substances contained in the wastewater is 300 mg / L or more. When the amount added is 100 mg / L to 500 mg / L
L. The divalent iron ion is characterized in that it is an iron chloride solution. Further, the present invention provides a method for removing boron in wastewater having a high salt concentration, wherein when the wastewater contains carbonates and organic substances, the pH of the wastewater is kept at 2 or less, and the pH of the wastewater is reduced by air aeration or vacuum deaeration. After removing carbon dioxide and removing activated organic matter by activated carbon adsorption, a solution containing magnesium ions is added to the wastewater, and then a sodium hydroxide solution is added to adjust the pH to 10.5-11.5. A method for removing boron from wastewater having a high salt concentration, comprising generating insoluble substances of boron, magnesium and magnesium, and removing boron by separating the insoluble substances.
【０００６】また、本発明の塩類濃度の高い排水中のほ
う素を除去する方法は、水酸化ナトリウム溶液を添加し
て調節するｐＨが、１０．７〜１１．２であることを特
徴とするものである。また、本発明の塩類濃度の高い排
水中のほう素を除去する方法は、マグネシウムイオンを
含む溶液が、塩化マグネシウム溶液又は硫酸マグネシウ
ム溶液であることを特徴とするものである。また、本発
明の塩類濃度の高い排水中のほう素を除去する方法は、
マグネシウムイオンを含む溶液のマグネシウムイオン量
が、排水中のほう素の重量比で３０〜７０倍であること
を特徴とするものである。The method for removing boron in wastewater having a high salt concentration according to the present invention is characterized in that the pH adjusted by adding a sodium hydroxide solution is 10.7-11.2. Things. The method for removing boron in wastewater having a high salt concentration according to the present invention is characterized in that the solution containing magnesium ions is a magnesium chloride solution or a magnesium sulfate solution. Further, the method for removing boron in wastewater having a high salt concentration according to the present invention comprises:
The amount of magnesium ions in the solution containing magnesium ions is 30 to 70 times the weight ratio of boron in the wastewater.
【０００７】[0007]
【作用】本発明の塩類濃度の高い排水中のほう素除去方
法は、排水にマグネシウムイオンを含む溶液を添加し、
次いで水酸化ナトリウム溶液を添加してｐＨ１０．５〜
１１．５、好ましくは１０．７〜１１．２に調節し、マ
グネシウムの水酸化物である、ほう素及びマグネシウム
の不溶解物質を生成させるものである。According to the method for removing boron in wastewater having a high salt concentration of the present invention, a solution containing magnesium ions is added to wastewater,
Then, sodium hydroxide solution is added to adjust the pH to 10.5 to
It is adjusted to 11.5, preferably 10.7-11.2, to produce insoluble substances of magnesium hydroxide, boron and magnesium.
【０００８】このｐＨの範囲で、ほう素は、解離しない
ほう酸（Ｈ３ＢＯ３）と解離によってマイナスイオンが
生ずるほう酸（Ｈ２ＢＯ３ −）が混在する。なお、解離
しないほう酸がＨＢＯ２として、解離によってマイナス
イオンが生ずるほう酸がＢＯ２ −として、これらが混在
する場合もある。また、マグネシウムイオンは、水酸化
物生成の初期に生ずるプラスを帯びた水酸化マグネシウ
ム（ＭｇＯＨ＋）と解離しない水酸化マグネシウム［Ｍ
ｇ（ＯＨ）２〕が混在する。水酸化ナトリウム溶液を加
えて、ｐＨ１０．５〜１１．５、好ましくは１０．７〜
１１．２に保持して、解離しないほう酸（Ｈ３ＢＯ３）
と解離によってマイナスイオンが生ずるほう酸（Ｈ２Ｂ
Ｏ３ −）、プラスを帯びた水酸化マグネシウム（ＭｇＯ
Ｈ＋）と解離しない水酸化マグネシウム（Ｍｇ（ＯＨ）
２）が、混在している溶液を攪拌することによって、マ
イナスイオンを帯びたほう酸（Ｈ２ＢＯ３ −）と、プラ
スを帯びた水酸化マグネシウム（ＭｇＯＨ＋）とが反応
して不溶解物質になると考えられる。また同時に、解離
しない水酸化マグネシウム（Ｍｇ（ＯＨ）２）に解離し
ないほう酸（Ｈ３ＢＯ３）を吸着させて共沈させると考
えられる。In this pH range, boron contains a mixture of boric acid (H 3 BO 3 ) that does not dissociate and boric acid (H 2 BO 3 − ) that generates negative ions by dissociation. In some cases, boric acid that does not dissociate is HBO 2 , and boric acid that generates a negative ion by dissociation is BO 2 − . In addition, magnesium ions are not dissociated from positively charged magnesium hydroxide (MgOH + ) generated in the early stage of hydroxide formation, and magnesium hydroxide [M
g (OH) 2 ]. Add sodium hydroxide solution and adjust the pH to 10.5 to 11.5, preferably 10.7 to 10.7.
11.2 Boric acid (H 3 BO 3 )
Boric acid (H 2 B
O 3 − ), plus magnesium hydroxide (MgO
H + ) and magnesium hydroxide that does not dissociate (Mg (OH)
2 ) By stirring the mixed solution, the boric acid (H 2 BO 3 − ) bearing anion and the magnesium hydroxide (MgOH + ) bearing a plus react with each other to form an insoluble substance. It is considered to be. At the same time, it is considered that boric acid (H 3 BO 3 ) that does not dissociate is adsorbed on magnesium hydroxide (Mg (OH) 2 ) that does not dissociate to cause coprecipitation.
【０００９】また、塩類濃度の高く炭酸塩を含む排水の
場合には、排水のｐＨを２以下に保ち空気曝気または真
空脱気して二酸化炭素を除去する処理を行った後に、マ
グネシウムイオンを含む溶液を添加し、次いで水酸化ナ
トリウム溶液を添加してｐＨ１０．５〜１１．５、好ま
しくは１０．７〜１１．２に調節し、マグネシウムの水
酸化物である、ほう素及びマグネシウムの不溶解物質を
生成させるものである。また、塩類濃度の高く炭酸塩及
び有機物を含む排水の場合には、排水のｐＨを２以下に
保ち空気曝気または真空脱気して二酸化炭素を除去する
処理を行った後に、マグネシウムイオンを含む溶液と２
価の鉄イオンを含む溶液を添加し、次いで水酸化ナトリ
ウム溶液を添加してｐＨ１０．５〜１１．５、好ましく
は１０．７〜１１．２に調節し、マグネシウムの水酸化
物である、ほう素及びマグネシウムの不溶解物質を生成
させるものである。In the case of wastewater containing a carbonate with a high salt concentration, the pH of the wastewater is kept at 2 or less, and after a treatment for removing carbon dioxide by air aeration or vacuum degassing, the wastewater contains magnesium ions. Add the solution and then adjust the pH to 10.5-11.5, preferably 10.7-11.2 by adding sodium hydroxide solution, and insoluble in the hydroxides of magnesium, boron and magnesium It produces substances. In the case of wastewater having a high salt concentration and containing carbonates and organic substances, after performing a treatment of removing carbon dioxide by keeping the pH of the wastewater at 2 or less and performing air aeration or vacuum degassing, a solution containing magnesium ions is used. And 2
A solution containing trivalent iron ions is added, and then a sodium hydroxide solution is added to adjust the pH to 10.5 to 11.5, preferably 10.1 to 11.2. It produces insoluble substances of elemental and magnesium.
【００１０】有機物を多く含む排水は生物処理が行われ
るが、この生物処理した後の排水には、多くの炭酸塩と
ある程度の有機物が含まれている。このような排水にマ
グネシウムイオンを含む溶液を添加すると、炭酸マグネ
シウムが形成されるだけで、本発明の意図するほう素の
処理には作用しない。そこで排水のｐＨを２以下に保
ち、空気曝気または真空脱気して二酸化炭素を除去する
ものである。炭酸塩はｐＨによってその存在が変わり、
アルカリ性では炭酸イオン（ＣＯ３ ２−）、中性では炭
酸水素イオン（ＨＣＯ３ −）、酸性で二酸化炭素（ＣＯ
２）の気体として存在するものであり、排水のｐＨを２
以下に保持することにより除去することかできるもので
ある。また、鉄イオンを含む溶液を添加することによっ
て有機物を吸着すると同時に有機物と化合しているほう
素も吸着されると考えられる。有機物の影響を少なくす
ることができるものである。Wastewater containing a large amount of organic matter is subjected to biological treatment, and the wastewater after the biological treatment contains many carbonates and some organic matter. When a solution containing magnesium ions is added to such wastewater, only magnesium carbonate is formed and does not affect the intended treatment of boron according to the present invention. Therefore, the pH of the wastewater is kept at 2 or less, and carbon dioxide is removed by air aeration or vacuum degassing. The presence of carbonate changes depending on pH,
Carbonic acid (CO 3 2− ) for alkaline, bicarbonate (HCO 3 − ) for neutral, and carbon dioxide (CO 3
2 ) exists as a gas, and the pH of the wastewater is adjusted to 2
It can be removed by holding below. Further, it is considered that by adding a solution containing iron ions, the organic substance is adsorbed, and at the same time, boron that is combined with the organic substance is also adsorbed. It can reduce the influence of organic matter.
【００１１】なお、先に提案しためっき排水中のほう素
除去法（特願平１１−２９９０２）、即ちめっき排水に
ニッケルイオン共存下でマグネシウムイオン、水酸化ナ
トリウム溶液を添加してｐＨ９．５〜１１に調節して不
溶化物として除去処理する方法により、塩類濃度の高い
排水、また塩類濃度が高く炭酸塩や有機物を含む排水を
処理しても、マグネシウムの水酸化物の生成が少なく、
ほう素及びマグネシウムの不溶解物質として除去するこ
とができない。そこで本発明は、先に提案しためっき排
水中のほう素除去方法とは、ニッケルイオン共存下では
ないこと、ｐＨ１０．５〜１１．５と高い範囲にしたこ
と、また炭酸塩や有機物を多く含む排水では、ｐＨを２
以下に保ち空気曝気または真空脱気の処理をすること、
２価の鉄イオンを含む溶液を添加すること等の相違する
工程により、塩類濃度の高い排水、また塩類濃度が高く
炭酸塩や有機物を含む排水中のほう素を、マグネシウム
の水酸化物であるほう素及びマグネシウムの不溶解物質
として生成させて除去したものである。The method for removing boron from plating wastewater proposed earlier (Japanese Patent Application No. 11-29902), that is, adding a magnesium ion and sodium hydroxide solution to a plating wastewater in the presence of nickel ions to obtain a pH of 9.5 to 9.5. According to the method of removing and treating as an insolubilized substance by adjusting to 11, even when treating wastewater having a high salt concentration or wastewater having a high salt concentration and containing carbonates and organic substances, the production of magnesium hydroxide is small,
It cannot be removed as an insoluble substance of boron and magnesium. Therefore, the present invention is different from the previously proposed method for removing boron in plating wastewater in that it is not in the presence of nickel ions, has a high pH range of 10.5 to 11.5, and contains a large amount of carbonates and organic substances. In the drainage, the pH is 2
Keep air aeration or vacuum deaeration below,
Through different processes such as adding a solution containing divalent iron ions, boron in wastewater with high salt concentration and wastewater with high salt concentration and containing carbonate and organic matter is converted into magnesium hydroxide. It is generated and removed as an insoluble substance of boron and magnesium.
【００１２】[0012]
【発明の実施の形態】表面処理排水や産業廃業物処分場
排水中には多種類の有害物質を含むため、複数の処理技
術を組み合わせて有害物質の処理が行われている。ほう
素の除去処理は、ある程度他の有害物質を処理した後で
除去した方が処理しやすい。しかし、有害物質の処理に
使用された薬品類によって、排水中の塩類濃度は高くな
っている。さらに、産業廃棄物処分場の排水のように有
機物が多い場合、生物処理が行われ有機物が二酸化炭素
と水に分解されるが、処理した水は、ｐＨが中性からア
ルカリ性であるため、炭酸塩がほぼ飽和状態で排水中に
含まれている。本発明は、このような塩類濃度が高く炭
酸塩及び有機物が含まれる排水中のほう素を除去処理す
るものである。DESCRIPTION OF THE PREFERRED EMBODIMENTS Since surface treatment wastewater and wastewater from industrial waste disposal sites contain many kinds of harmful substances, harmful substances are treated by combining a plurality of treatment techniques. It is easier to remove boron after treating other harmful substances to some extent. However, due to the chemicals used to treat harmful substances, the salt concentration in the wastewater is high. Furthermore, when there is a large amount of organic matter such as wastewater from an industrial waste disposal site, biological treatment is performed and the organic matter is decomposed into carbon dioxide and water.However, the pH of the treated water is neutral to alkaline, Salt is almost saturated and contained in wastewater. The present invention is to remove boron in wastewater containing such a high salt concentration and containing carbonates and organic substances.
【００１３】本願発明が、ほう素除去をしようとする塩
類濃度の高い排水とは、例えば、排水処理後の処理排水
中に主に溶解している硫酸ナトリウム、塩化ナトリウム
のような塩類を含むものである。これは、銅、亜鉛、ニ
ッケルなどの重金属の有害物質の処理に使用される水酸
化ナトリウム、硫酸、塩酸によって処理反応で硫酸ナト
リウムや塩化ナトリウムが生成し、処理後の排水中に溶
存して塩類の濃度が高くなっている。具体的には電気伝
導率として５００ｍＳ（ジーメンス）／ｍ以上となるよ
うな塩類を含んでいるものである。また排水に含まれる
有機物については、酢酸、シュウ酸、クエン酸等の有機
酸、高分子化合物、アミノ酸のようなものを含むもので
あり、全有機炭素量として３００ｍｇＣ／Ｌ以上の有機
物を含むものでは、鉄イオンを含む溶液の添加、活性炭
吸着処理を行うものである。In the present invention, the wastewater having a high salt concentration for removing boron includes, for example, salts such as sodium sulfate and sodium chloride which are mainly dissolved in the treated wastewater after the wastewater treatment. . This is because sodium sulfate, sulfuric acid, and hydrochloric acid used to treat harmful substances of heavy metals such as copper, zinc, and nickel produce sodium sulfate and sodium chloride in the treatment reaction, which are dissolved in the treated wastewater to form salts. Concentration is high. Specifically, it contains a salt having an electric conductivity of 500 mS (Siemens) / m or more. The organic matter contained in the wastewater includes organic acids such as acetic acid, oxalic acid, and citric acid, polymer compounds, and amino acids, and includes organic substances having a total organic carbon amount of 300 mgC / L or more. In this method, a solution containing iron ions is added, and activated carbon adsorption treatment is performed.
【００１４】本発明の排水中のほう素の処理方法につい
て、具体的に示せば、塩類濃度の高い排水に塩化マグネ
シウム又は硫酸マグネシウム溶液を添加し、５〜１０％
の水酸化ナトリウム溶液でｐＨを１０．５〜１１．５、
好ましくは１０．７〜１１．２に調節し、１０分間攪拌
し、不溶解物質を生成させ、凝集沈殿法によって固液分
離してほう素を除去処理するものである。塩類濃度が高
く炭酸塩を含む排水には、硫酸溶液を添加してｐＨを２
以下に保ち、３０分間空気曝気あるいは真空脱気して二
酸化炭素を除去し、塩化マグネシウム又は硫酸マグネシ
ウム溶液を添加し、５〜１０％の水酸化ナトリウム溶液
でｐＨを１０．５〜１１．５、好ましくは１０．７〜１
１．２に調節し、１０分間攪拌し、不溶解物質を生成さ
せ、凝集沈殿法によって固液分離してほう素を除去処理
するものである。また、塩類濃度が高く有機物及び炭酸
塩を含む排水には、硫酸溶液を添加してｐＨを２以下に
保ち、３０分間空気曝気あるいは真空脱気して二酸化炭
素を除去し、塩化鉄溶液と塩化マグネシウム又は塩化鉄
溶液と硫酸マグネシウム溶液を添加し、５〜１０％の水
酸化ナトリウム溶液でｐＨを１０．５〜１１．５、好ま
しくは１０．７〜１１．２に調節し、１０分間攪拌し、
不溶解物質を生成させ、凝集沈殿法によって固液分離し
てほう素を除去処理するものである。More specifically, the method for treating boron in wastewater of the present invention is to add magnesium chloride or magnesium sulfate solution to wastewater with high salt concentration,
PH of 10.5 to 11.5 with sodium hydroxide solution of
Preferably, the concentration is adjusted to 10.7-11.2, and the mixture is stirred for 10 minutes to generate an insoluble substance, and solid-liquid separation is performed by a coagulation sedimentation method to remove boron. Sulfuric acid solution is added to wastewater with high salt concentration and containing carbonate to adjust the pH to 2
Keep below, and remove carbon dioxide by air aeration or vacuum degassing for 30 minutes, add magnesium chloride or magnesium sulfate solution, and adjust the pH to 10.5-11.5 with 5-10% sodium hydroxide solution. Preferably 10.7-1
The mixture is adjusted to 1.2, stirred for 10 minutes to generate an insoluble substance, and subjected to solid-liquid separation by a coagulation sedimentation method to remove boron. In addition, sulfuric acid solution is added to the wastewater containing a high salt concentration and containing organic substances and carbonates to keep the pH at 2 or less, and the carbon dioxide is removed by air aeration or vacuum degassing for 30 minutes. Add a magnesium or iron chloride solution and a magnesium sulfate solution, adjust the pH to 10.5-11.5, preferably 10.7-11.2 with a 5-10% sodium hydroxide solution, and stir for 10 minutes. ,
An insoluble substance is generated, and solid-liquid separation is performed by a coagulation sedimentation method to remove boron.
【００１５】また、塩類濃度が高く有機物及び炭酸塩を
含む排水であって、全有機炭素量として３００ｍｇＣ／
Ｌ以上の有機物を含む排水には、硫酸溶液を添加してｐ
Ｈを２以下に保ち、３０分間空気曝気あるいは真空脱気
して二酸化炭素を除去し、そして添加する塩化鉄溶液と
塩化マグネシウム又は塩化鉄溶液と硫酸マグネシウム溶
液については、２価の鉄イオンを含む溶液を１００ｍｇ
／Ｌ〜５００ｍｇ／Ｌ添加する。次いで５〜１０％の水
酸化ナトリウム溶液でｐＨを１０．５〜１１．５に調節
して、共沈法によってほう素、鉄及びマグネシウムの不
溶解物を生成させ、固液分離して有機物を含む排水中の
ほう素を除去処理するものである。また、マグネシウム
イオンを含む溶液のマグネシウムイオン量が、排水中の
ほう素の重量比で３０〜７０倍であることが好ましく、
５〜１０％水酸化ナトリウム溶液を添加してｐＨ１０．
５〜１１．５に調節し、撹拌することにより、排水中に
ふくまれているほう素のほとんどが、マグネシウムと不
溶解物質である水酸化物を生成するものである。また、
活性炭吸着処理は、塩類濃度が高く有機物及び炭酸塩を
含む排水の有機物を活性炭に吸着させるもので、排水を
粒状・粉状の活性炭の層を通して処理するもの、排水に
粉状・粒状の活性炭を添加して吸着処理するものであ
る。[0015] The wastewater having a high salt concentration and containing organic substances and carbonates has a total organic carbon content of 300 mgC /
To wastewater containing organic substances of L or more, add a sulfuric acid solution and add p
Keep H at 2 or less, remove the carbon dioxide by air aeration or vacuum degassing for 30 minutes, and add divalent iron ions to the added iron chloride solution and magnesium chloride or the iron chloride solution and magnesium sulfate solution. 100 mg of solution
/ L to 500 mg / L. Then, the pH is adjusted to 10.5 to 11.5 with a 5 to 10% sodium hydroxide solution, and insolubles of boron, iron, and magnesium are generated by a coprecipitation method. It removes boron in wastewater containing water. Further, the amount of magnesium ions in the solution containing magnesium ions is preferably 30 to 70 times by weight of boron in the wastewater,
Add 5-10% sodium hydroxide solution to pH10.
By adjusting to 5 to 11.5 and stirring, most of the boron contained in the wastewater produces magnesium and hydroxide which is an insoluble substance. Also,
Activated carbon adsorption treatment is to adsorb organic matter in wastewater containing high organic matter and carbonates with high salt concentration to activated carbon. It is added and subjected to adsorption treatment.
【００１６】[0016]
【実施例１】本発明の実施例について具体的データーを
示し説明する。ほう素の除去処理しようとする排水の水
質は、ｐＨ７．３、電気伝導率１０６２ｍＳ／ｍ、全有
機炭素量、２０ｍｇＣ／Ｌ、ほう素量９．６ｍｇＢ／Ｌ
を含む産業廃棄物処分場浸出水処理放流水で、この塩類
濃度の高い排水中のほう素の処理について説明する。こ
の排水２００ｍｌに塩化マグネシウム溶液を３ｇ／Ｌの
割合で添加し、１０％の水酸化ナトリウム溶液で、ｐＨ
を１０．７〜１１．０に調節し、１０分間維持して不溶
解物質を生成させ、ろ紙５Ｃを用いて固液分離をした。
その結果、排水中に９．６ｍｇＢ／Ｌ含まれていたほう
素が除去処理により、１．０ｍｇＢ／Ｌに減少した。比
較例として、同じ排水２００ｍｌに、ニッケルイオン共
存下で塩化マグネシウム溶液を３ｇ／Ｌの割合で添加
し、１０％の水酸化ナトリウム溶液でｐＨを１０前後に
調節し、１０分間維持して不溶解物質を生成させ、ろ紙
３Ｃを用いて固液分離をした。その結果、マグネシウム
の水酸化物の生成も少なくほう素を除去するこができな
かった。Embodiment 1 An embodiment of the present invention will be described with reference to specific data. The water quality of the wastewater to be subjected to the boron removal treatment is pH 7.3, electric conductivity 1062 mS / m, total organic carbon content, 20 mgC / L, and boron content 9.6 mgB / L.
The treatment of boron in wastewater with a high salt concentration in the effluent from the leachate treatment at an industrial waste disposal site that contains Magnesium chloride solution was added to 200 ml of the drainage at a rate of 3 g / L, and the pH was adjusted with a 10% sodium hydroxide solution.
Was adjusted to 10.7-11.0, and maintained for 10 minutes to generate an insoluble substance, followed by solid-liquid separation using a filter paper 5C.
As a result, boron which had been contained in the waste water at 9.6 mgB / L was reduced to 1.0 mgB / L by the removal treatment. As a comparative example, a magnesium chloride solution was added to 200 ml of the same wastewater in the presence of nickel ions at a rate of 3 g / L, the pH was adjusted to about 10 with a 10% sodium hydroxide solution, and the solution was maintained for 10 minutes to be insoluble. A substance was generated, and solid-liquid separation was performed using filter paper 3C. As a result, generation of magnesium hydroxide was small and boron could not be removed.
【００１７】[0017]
【実施例２】排水水質としてｐＨ６．６、電気伝導率１
０００ｍＳ／ｍ、全有機炭素量２０ｍｇＣ／Ｌ、ニッケ
ルイオン量５００ｍｇ／Ｌ、ほう素量６１ｍｇＢ／Ｌを
含むめっき総合排水処理工程の排水の塩類濃度の高い排
水中のほう素の処理について説明する。この排水２００
ｍｌに塩化マグネシウム溶液を３ｇ／Ｌの割合で添加
し、１０％の水酸化ナトリウム溶液でｐＨを１０．８〜
１１．０に調節し、１０分間維持して不溶解物質を生成
させ、ろ紙５Ｃを用いて固液分離をした。その結果、排
水中に６１ｍｇＢ／Ｌ含まれていたほう素を、７ｍｇＢ
／Ｌに除去することができた。比較例として、同じ排水
２００ｍｌに、ニッケルイオン共存下で塩化マグネシウ
ム溶液を３ｇ／Ｌの割合で添加し、１０％の水酸化ナト
リウム溶液でｐＨを１０前後に調節し、１０分間維持し
て不溶解物質を生成させ、ろ紙５Ｃを用いて固液分離を
した。その結果、マグネシウムの水酸化物の生成も少な
くほう素３６ｍｇＢ／Ｌまでにしか除去することがきな
かった。Example 2 Wastewater quality is pH 6.6, electric conductivity 1
The treatment of boron in the wastewater having a high salt concentration in the wastewater in the comprehensive plating wastewater treatment step including 000 mS / m, total organic carbon content of 20 mgC / L, nickel ion content of 500 mg / L, and boron content of 61 mgB / L will be described. This drainage 200
To the resulting solution, a magnesium chloride solution was added at a rate of 3 g / L, and the pH was adjusted to 10.8 to 10% with a sodium hydroxide solution.
It was adjusted to 11.0 and maintained for 10 minutes to generate insoluble substances, and then subjected to solid-liquid separation using filter paper 5C. As a result, 61 mgB / L of boron in the wastewater was changed to 7 mgB / L.
/ L. As a comparative example, a magnesium chloride solution was added to 200 ml of the same wastewater in the presence of nickel ions at a rate of 3 g / L, the pH was adjusted to about 10 with a 10% sodium hydroxide solution, and the solution was maintained for 10 minutes to be insoluble. A substance was generated, and solid-liquid separation was performed using filter paper 5C. As a result, generation of magnesium hydroxide was small and boron could be removed only up to 36 mgB / L.
【００１８】[0018]
【実施例３】排水水質としてｐＨ８．４、電気伝導率９
８３ｍＳ／ｍ、全炭素量２１２ｍｇＣ／Ｌ、全有機炭素
量４９ｍｇＣ／Ｌ、ほう素量１５ｍｇＢ／Ｌを含む産業
廃棄物処分場浸出水処理工程水（生物処理後水）の塩類
濃度が高く炭酸塩の多い排水中のほう素の処理について
説明する。排水に硫酸溶液を添加してｐＨを２以下に保
ち、３０分間曝気して二酸化炭素を除去した。その後、
排水２００ｍｌに塩化マグネシウム溶液を３ｇ／Ｌの割
合で添加し、水酸化ナトリウム溶液でｐＨを１０．７〜
１１．０に調節し、１０分間維持して不溶解物質を生成
させ、ろ紙５Ｃを用いて固液分離をした。その結果、排
水中に１５ｍｇＢ／Ｌを含まれるほう素が、１．３ｍｇ
Ｂ／Ｌに除去処理された。Example 3 Wastewater quality is pH 8.4 and electric conductivity 9
83mS / m, total carbon content 212mgC / L, total organic carbon content 49mgC / L, boron content 15mgB / L, industrial salt disposal site leachate treatment process water (water after biological treatment) has high salt concentration and carbonate. The treatment of boron in wastewater with a large amount will be described. A sulfuric acid solution was added to the wastewater to keep the pH at 2 or less, and aeration was performed for 30 minutes to remove carbon dioxide. afterwards,
Magnesium chloride solution was added to 200 ml of drainage at a rate of 3 g / L, and the pH was adjusted to 10.7 to 1 with sodium hydroxide solution.
It was adjusted to 11.0 and maintained for 10 minutes to generate insoluble substances, and then subjected to solid-liquid separation using filter paper 5C. As a result, 1.3 mg of boron containing 15 mgB / L in the waste water was obtained.
B / L was removed.
【００１９】[0019]
【実施例４】排水水質としてｐＨ８．２、電気伝導率９
１０ｍＳ／ｍ、全炭素量１０００ｍｇＣ／Ｌ、全有機炭
素量３００ｍｇＣ／Ｌ、ほう素量７５ｍｇＢ／Ｌを含む
産業廃棄物処分場浸出水の塩類濃度が高く炭酸塩及び有
機物が多い排水中のほう素の処理について説明する。排
水に硫酸溶液を添加してｐＨを２以下に保ち、３００分
間空気曝気して二酸化炭素を除去した。その後、排水２
００ｍｌに塩化鉄溶液を１００ｍｇ／Ｌと塩化マグネシ
ウム溶液を３ｇ／Ｌの割合で添加し、水酸化ナトリウム
溶液でｐＨを１０．７〜１１．０に調節し、１０分間維
持して不溶解物質を生成させ、ろ紙５Ｃを用いて固液分
離をした。その結果排水中に７５ｍｇＢ／Ｌを含まれる
ほう素が、１２ｍｇＢ／Ｌに除去処理された。Example 4 Wastewater quality: pH 8.2, electric conductivity 9
Boron in effluent containing 10mS / m, total carbon content 1000mgC / L, total organic carbon content 300mgC / L, boron content 75mgB / L, having high salt concentration and high carbonate and organic matter in the leachate of industrial waste disposal site leachate Will be described. A sulfuric acid solution was added to the wastewater to keep the pH at 2 or less, and air was aerated for 300 minutes to remove carbon dioxide. Then drain 2
100 mg / L of iron chloride solution and 3 g / L of magnesium chloride solution are added to 00 ml, pH is adjusted to 10.7-11.0 with sodium hydroxide solution, and maintained for 10 minutes to remove insoluble substances. Then, solid-liquid separation was performed using the filter paper 5C. As a result, boron containing 75 mgB / L in the wastewater was removed to 12 mgB / L.
【００２０】[0020]
【実施例５】実施例５は、上記実施例４と同様の産業廃
棄物処分場浸出水について有機物を活性炭処理した排水
中のほう素の除去処理を行ったものである。排水に硫酸
溶液を添加してｐＨを２以下に保ち、３０分間空気曝気
して二酸化炭素を除去した。その後、活性炭吸着処理を
行い全有機炭素量３００ｍｇＣ／Ｌを３０ｍｇＣ／Ｌに
した。炭酸及び有機物を除去処理した排水２００ｍｌに
塩化マグネシウム溶液を３ｇ／Ｌの割合で添加し、水酸
化ナトリウム溶液でｐＨを１０．７〜１１．０に調節
し、１０分間維持して不溶解物質を生成させ、ろ紙５Ｃ
を用いて固液分離をした。その結果、排水中に７５ｍｇ
Ｂ／Ｌを含まれるほう素が、１１ｍｇＢ／Ｌに除去処理
された。Fifth Embodiment In a fifth embodiment, the same treatment as in the fourth embodiment is carried out to remove boron from the effluent of an industrial waste disposal site by subjecting organic substances to activated carbon treatment. A sulfuric acid solution was added to the wastewater to keep the pH at 2 or less, and air was aerated for 30 minutes to remove carbon dioxide. Thereafter, activated carbon adsorption treatment was performed to reduce the total organic carbon amount from 300 mgC / L to 30 mgC / L. Magnesium chloride solution was added at a rate of 3 g / L to 200 ml of wastewater from which carbon dioxide and organic substances were removed, the pH was adjusted to 10.7-11.0 with sodium hydroxide solution, and maintained for 10 minutes to remove insoluble substances. Generate, filter paper 5C
Was used to perform solid-liquid separation. As a result, 75 mg
Boron containing B / L was removed to 11 mgB / L.
【００２１】[0021]
【発明の効果】以上説明したように、本発明によれば、
塩類濃度の高い排水中のほう素を除去するには、マグネ
シウムイオンを含む溶液を添加して水酸化ナトリウム溶
液でｐＨを１０．５〜１１．５、好ましくは１０．７〜
１１．２に調節し、共沈法によってほう素及びマグネシ
ウムの不溶解物質を生成させ、これを固液分離すること
により効果的に、かつ充分にほう素を除去することがで
きるという効果を有する。また、塩類濃度の高く、有機
物及び炭酸塩を含む排水は、ｐＨを２以下に保って空気
曝気あるいは真空脱気によって二酸化炭素を除去し、有
機物の影響を防ぐために２価の鉄イオン溶液を添加し、
共沈剤としてマグネシウムイオンを添加し、水酸化ナト
リウム溶液でｐＨを１０．７〜１１．２に調節し、共沈
法によってほう素、マグネシウム及び鉄の不溶解物質を
生成させ、これを固液分離し、効果的に、かつ充分にほ
う素を除去することができるという効果を奏するもので
ある。As described above, according to the present invention,
To remove boron in wastewater having a high salt concentration, a solution containing magnesium ions is added, and the pH is adjusted to 10.5 to 11.5, preferably 10.7 to 1 with a sodium hydroxide solution.
Adjusted to 11.2, an insoluble substance of boron and magnesium is produced by the coprecipitation method, and the solid-liquid separation has the effect that boron can be effectively and sufficiently removed. . In addition, wastewater containing a high concentration of salts and containing organic substances and carbonates removes carbon dioxide by air aeration or vacuum degassing while maintaining the pH at 2 or less, and a divalent iron ion solution is added to prevent the influence of organic substances. And
Magnesium ions are added as a coprecipitant, the pH is adjusted to 10.7-11.2 with a sodium hydroxide solution, and boron, magnesium and iron insolubles are formed by a coprecipitation method. The effect is that boron can be separated, and boron can be effectively and sufficiently removed.
Claims (9)
方法において、前記排水にマグネシウムイオンを含む溶
液を添加し、次いで水酸化ナトリウム溶液を添加してｐ
Ｈ１０．５〜１１．５に調節し、ほう素及びマグネシウ
ムの不溶解物質を生成させ、前記不溶解物質を分離する
ことによりほう素を除去することを特徴とする塩類濃度
の高い排水中のほう素除去方法。In a method for removing boron in wastewater having a high salt concentration, a solution containing magnesium ions is added to the wastewater, and then a sodium hydroxide solution is added to the wastewater.
H10.5 to 11.5 to produce boron and magnesium insolubles, and to remove boron by separating the insolubles. Element removal method.
方法において、排水が炭酸塩を含む場合には、前記排水
のｐＨを２以下に保ち空気曝気または真空脱気して二酸
化炭素を除去する処理を行った後に、排水にマグネシウ
ムイオンを含む溶液を添加し、次いで水酸化ナトリウム
溶液を添加してｐＨ１０．５〜１１．５に調節し、ほう
素及びマグネシウムの不溶解物質を生成させ、前記不溶
解物質を分離することによりほう素を除去することを特
徴とする塩類濃度の高い排水中のほう素除去方法。2. A method for removing boron in wastewater having a high salt concentration, wherein when the wastewater contains a carbonate, the pH of the wastewater is kept at 2 or less, and the carbon dioxide is removed by air aeration or vacuum degassing. After the removal treatment, a solution containing magnesium ions is added to the waste water, and then a sodium hydroxide solution is added to adjust the pH to 10.5 to 11.5 to form insoluble substances of boron and magnesium. And removing boron by separating the insoluble substance from the wastewater, the method comprising removing boron from wastewater having a high salt concentration.
方法において、排水が炭酸塩及び有機物を含む場合に
は、前記排水のｐＨを２以下に保ち空気曝気または真空
脱気して二酸化炭素を除去する処理を行った後に、排水
にマグネシウムイオンを含む溶液と２価の鉄イオンを含
む溶液を添加し、次いで水酸化ナトリウム溶液を添加し
てｐＨ１０．５〜１１．５に調節し、ほう素及びマグネ
シウムの不溶解物質を生成させ、前記不溶解物質を分離
することによりほう素を除去することを特徴とする塩類
濃度の高い排水中のほう素除去方法。3. A method for removing boron in wastewater having a high salt concentration, wherein when the wastewater contains carbonate and organic substances, the pH of the wastewater is kept at 2 or less, and the pH of the wastewater is reduced by air aeration or vacuum deaeration. After performing the treatment for removing carbon, a solution containing magnesium ions and a solution containing divalent iron ions are added to the wastewater, and then a sodium hydroxide solution is added to adjust the pH to 10.5-11.5. A method for removing boron from wastewater having a high salt concentration, comprising generating an insoluble substance of boron and magnesium and removing boron by separating the insoluble substance.
ｍｇ／Ｌ以上の場合には、２価の鉄イオンを含む溶液の
添加量が、１００ｍｇ／Ｌ〜５００ｍｇ／Ｌであること
を特徴とする請求項３に記載の塩類濃度の高い排水中の
ほう素除去方法。4. The organic matter contained in the waste water has a total carbon content of 300.
The amount in the wastewater having a high salt concentration according to claim 3, wherein the amount of the solution containing divalent iron ions is 100 mg / L to 500 mg / L when the concentration is not less than mg / L. Element removal method.
を特徴とする請求項３又は４に記載の塩類濃度の高い排
水中のほう素除去方法。5. The method for removing boron in wastewater having a high salt concentration according to claim 3, wherein the divalent iron ion is an iron chloride solution.
方法において、排水が炭酸塩及び有機物を含む場合に
は、前記排水のｐＨを２以下に保ち空気曝気または真空
脱気して二酸化炭素を除去する処理、活性炭吸着処理し
て有機物を除去を行った後に、排水にマグネシウムイオ
ンを含む溶液を添加し、次いで水酸化ナトリウム溶液を
添加してｐＨ１０．５〜１１．５に調節し、ほう素及び
マグネシウムの不溶解物質を生成させ、前記不溶解物質
を分離することによりほう素を除去することを特徴とす
る塩類濃度の高い排水中のほう素除去方法。6. A method for removing boron in wastewater having a high salt concentration, wherein when the wastewater contains carbonate and organic substances, the pH of the wastewater is kept at 2 or less, and the pH of the wastewater is reduced by aeration with air or vacuum deaeration. After removing carbon and organic matter by activated carbon adsorption treatment, a solution containing magnesium ions is added to the wastewater, and then a sodium hydroxide solution is added to adjust the pH to 10.5-11.5. A method for removing boron from wastewater having a high salt concentration, comprising generating an insoluble substance of boron and magnesium and removing boron by separating the insoluble substance.
ｐＨが、１０．７〜１１．２であることを特徴とする請
求項１〜６のいずれかに記載の塩類濃度の高い排水中の
ほう素除去方法。7. The wastewater having a high salt concentration according to claim 1, wherein the pH adjusted by adding a sodium hydroxide solution is 10.7-11.2. Boron removal method.
グネシウム溶液又は硫酸マグネシウム溶液であることを
特徴とする請求項１〜７のいずれかに記載の塩類濃度の
高い排水中のほう素除去方法。8. The method for removing boron from wastewater having a high salt concentration according to claim 1, wherein the solution containing magnesium ions is a magnesium chloride solution or a magnesium sulfate solution.
ウムイオン量が、排水中のほう素の重量比で３０〜７０
倍であることを特徴とする請求項１〜７のいずれかに記
載の塩類濃度の高い排水中のほう素除去方法。9. The amount of magnesium ions in the solution containing magnesium ions is from 30 to 70 by weight of boron in the waste water.
The method for removing boron in wastewater having a high salt concentration according to any one of claims 1 to 7, wherein the concentration is twice as high.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000036739A JP3284347B2 (en) | 2000-02-15 | 2000-02-15 | Removal of boron from wastewater with high salt concentration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000036739A JP3284347B2 (en) | 2000-02-15 | 2000-02-15 | Removal of boron from wastewater with high salt concentration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001225081A true JP2001225081A (en) | 2001-08-21 |
| JP3284347B2 JP3284347B2 (en) | 2002-05-20 |
Family
ID=18560746
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000036739A Expired - Fee Related JP3284347B2 (en) | 2000-02-15 | 2000-02-15 | Removal of boron from wastewater with high salt concentration |
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| Country | Link |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009082843A (en) * | 2007-10-01 | 2009-04-23 | Maezawa Ind Inc | Boron removal method |
| JP2013203642A (en) * | 2012-03-29 | 2013-10-07 | Solt Industry Center Of Japan | Method for recovering boron |
| JP2014028372A (en) * | 2008-01-31 | 2014-02-13 | Solvay (Sa) | Method for decomposing organic substances within aqueous composition |
| WO2014196132A1 (en) * | 2013-06-03 | 2014-12-11 | 三菱電機株式会社 | Method and device for treating boron-containing water |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332753C (en) * | 2005-06-20 | 2007-08-22 | 天津化工研究设计院 | Sulphur resisting catalyzing deoxidation agent and its production process |
-
2000
- 2000-02-15 JP JP2000036739A patent/JP3284347B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009082843A (en) * | 2007-10-01 | 2009-04-23 | Maezawa Ind Inc | Boron removal method |
| JP2014028372A (en) * | 2008-01-31 | 2014-02-13 | Solvay (Sa) | Method for decomposing organic substances within aqueous composition |
| JP2013203642A (en) * | 2012-03-29 | 2013-10-07 | Solt Industry Center Of Japan | Method for recovering boron |
| WO2014196132A1 (en) * | 2013-06-03 | 2014-12-11 | 三菱電機株式会社 | Method and device for treating boron-containing water |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3284347B2 (en) | 2002-05-20 |
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