JP3336858B2 - Method for treating boron-containing water - Google Patents
Method for treating boron-containing waterInfo
- Publication number
- JP3336858B2 JP3336858B2 JP13360696A JP13360696A JP3336858B2 JP 3336858 B2 JP3336858 B2 JP 3336858B2 JP 13360696 A JP13360696 A JP 13360696A JP 13360696 A JP13360696 A JP 13360696A JP 3336858 B2 JP3336858 B2 JP 3336858B2
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- JP
- Japan
- Prior art keywords
- boron
- extraction
- extractant
- extracting agent
- containing water
- 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.)
- Expired - Fee Related
Links
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- Treatment Of Water By Ion Exchange (AREA)
- Physical Water Treatments (AREA)
- Removal Of Specific Substances (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明はホウ素含有水の処理
方法に係り、特に、ホウ素含有水をイオン交換樹脂で処
理する方法において、イオン交換樹脂の再生廃液からホ
ウ素を抽出し、更に、ホウ素を抽出した抽出剤からホウ
素を効率的に逆抽出して回収する方法に関する。The present invention relates to a method for treating boron-containing water, and more particularly to a method for treating boron-containing water with an ion-exchange resin. The present invention relates to a method for efficiently back-extracting and recovering boron from an extracted extractant.
【０００２】[0002]
【従来の技術】ホウ素化合物は、医薬、化粧品原料、石
鹸工業、電気メッキ等の種々の分野で幅広く利用されて
おり、これらの製造工程からはホウ素化合物を含有する
廃水が排出される。また、原子力発電所から発生する放
射性廃液、地熱発電廃水、あるいは排煙脱硫又は脱硝廃
水、ゴミ焼却洗煙廃水等にもホウ素化合物が含まれてい
る。2. Description of the Related Art Boron compounds are widely used in various fields such as pharmaceuticals, cosmetic raw materials, soap industry, electroplating and the like, and wastewater containing boron compounds is discharged from these production processes. Further, boron compounds are also contained in radioactive waste liquid, geothermal power generation wastewater, flue gas desulfurization or denitrification wastewater, garbage incineration smoke and wastewater generated from nuclear power plants.
【０００３】これらのホウ素含有水の処理方法として、
イオン交換樹脂によりホウ素を吸着除去する方法が知ら
れている。そして、このホウ素を吸着したイオン交換樹
脂を酸と接触させて再生するに当たり、再生廃液を抽出
剤と接触させてホウ素を抽出し、抽残液をアニオン交換
樹脂の再生用液として再利用する方法が提案されている
（特公平１−５０４７６号公報）。As a method for treating these boron-containing waters,
A method of adsorbing and removing boron with an ion exchange resin is known. Then, upon regenerating the ion-exchange resin adsorbed with boron by contacting it with an acid, the regenerated waste liquid is brought into contact with an extractant to extract boron, and the raffinate is reused as a liquid for regeneration of the anion-exchange resin. (Japanese Patent Publication No. 1-50476).
【０００４】この特公平１−５０４７６号公報では、抽
出剤として、オクチレングリコール、２−エチルヘキサ
ノール、４−ｔ−ブチルカテコール等を用いる。また、
ホウ素を抽出した抽出剤を、水酸化ナトリウム（ＮａＯ
Ｈ）水溶液、炭酸ナトリウム（Ｎａ2 ＣＯ3 ）水溶液等
の逆抽出剤と接触させてホウ素を逆抽出し、更に、ホウ
素を逆抽出した逆抽出剤からホウ素を晶析させて回収す
る。In Japanese Patent Publication No. 1-50476, octylene glycol, 2-ethylhexanol, 4-t-butylcatechol and the like are used as an extractant. Also,
The extractant from which boron was extracted was replaced with sodium hydroxide (NaO).
H) The boron is back-extracted by contacting with a back-extracting agent such as an aqueous solution or an aqueous solution of sodium carbonate (Na 2 CO 3 ), and the boron is crystallized and recovered from the back-extracting agent obtained by back-extracting boron.
【０００５】[0005]
【発明が解決しようとする課題】上記特公平１−５０４
７６号公報では、ホウ素を抽出した抽出剤を逆抽出する
際の好適な逆抽出条件や、ホウ素を逆抽出した逆抽出剤
からホウ素を晶析回収する際の好適な晶析条件が明らか
にされておらず、十分な逆抽出ないし晶析効率が得られ
ない場合があった。Problems to be Solved by the Invention
In Patent Publication No. 76, suitable back-extraction conditions when back-extracting the extracting agent from which boron is extracted, and suitable crystallization conditions when crystallizing and recovering boron from the back-extracting agent after back-extracting boron are clarified. In some cases, sufficient back extraction or crystallization efficiency could not be obtained.
【０００６】本発明は上記従来の実状に鑑みてなされた
ものであって、ホウ素含有水をイオン交換樹脂と接触さ
せて処理した後のイオン交換樹脂の再生廃液から、ホウ
素を効率的に抽出すると共に、ホウ素を抽出した抽出剤
からホウ素を効率的に逆抽出し、更に、ホウ素を逆抽出
した逆抽出剤から、ホウ素を効率的に晶析させて回収す
ることができるホウ素含有水の処理方法を提供すること
を目的とする。The present invention has been made in view of the above-mentioned conventional situation, and efficiently extracts boron from a regenerated waste liquid of an ion-exchange resin after treating by contacting boron-containing water with the ion-exchange resin. A method for treating boron-containing water that can efficiently back-extract boron from an extractant from which boron has been extracted and further efficiently crystallize and recover boron from the back-extractant that has back-extracted boron. The purpose is to provide.
【０００７】[0007]
【課題を解決するための手段】請求項１のホウ素含有水
の処理方法は、ホウ素含有水をイオン交換樹脂と接触さ
せた後、該イオン交換樹脂を酸と接触させて再生し、こ
の再生廃液を抽出剤と接触させてホウ素を抽出した後、
ホウ素を抽出した抽出剤を逆抽出剤と接触させてホウ素
を逆抽出するホウ素含有水の処理方法において、前記逆
抽出剤としてｐＨ１２．５以上の逆抽出剤を用いること
を特徴とする。According to a first aspect of the present invention, there is provided a method for treating boron-containing water, comprising the steps of: contacting boron-containing water with an ion-exchange resin; and then contacting the ion-exchange resin with an acid for regeneration. After contacting with an extractant to extract boron,
A method for treating boron-containing water in which a boron-extracting agent is brought into contact with a back-extracting agent to back-extract boron, wherein a back-extracting agent having a pH of 12.5 or more is used as the back-extracting agent.
【０００８】請求項２のホウ素含有水の処理方法は、請
求項１の方法において、ホウ素を逆抽出した逆抽出剤に
酸を添加してホウ素を晶析させることを特徴とする。[0008] The method of treating boron-containing water according to claim 2 is characterized in that, in the method of claim 1, an acid is added to a back-extracting agent obtained by back-extracting boron to crystallize boron.
【０００９】種々の研究の結果、ホウ素を処理したイオ
ン交換樹脂の再生廃液からホウ素を抽出し、このホウ素
を抽出した抽出剤からホウ素を逆抽出する場合、逆抽出
剤のｐＨが逆抽出効率に大きく影響することが見出され
た。本発明に従って、ｐＨ１２．５以上の逆抽出剤を用
いることにより、ホウ素を効率的に逆抽出することがで
きる。[0009] As a result of various studies, when boron is extracted from the waste liquid of the ion-exchange resin treated with boron, and the boron is back-extracted from the extracting agent from which the boron is extracted, the pH of the back-extracting agent increases the back extraction efficiency. It has been found to have a significant effect. According to the present invention, boron can be efficiently back-extracted by using a back-extracting agent having a pH of 12.5 or more.
【００１０】このように、比較的ｐＨの高い逆抽出剤を
用いることで、ホウ素の逆抽出効率が向上する理由は、
逆抽出機構が、下記式の如く、抽出剤中のホウ酸と、逆
抽出剤中のアルカリとの反応よりなり、逆抽出効率は、
アルカリ濃度が高い程向上するためと推定される。As described above, the reason why the efficiency of back extraction of boron is improved by using a back extraction agent having a relatively high pH is as follows.
The back-extraction mechanism consists of a reaction between boric acid in the extractant and an alkali in the back-extractant, as shown in the following formula.
It is presumed that the higher the alkali concentration, the better.
【００１１】４Ｈ3 ＢＯ3 ＋２ＮａＯＨ＋３Ｈ2 Ｏ→Ｎ
ａ2 Ｂ4 Ｏ7 ・１０Ｈ2 Ｏ また、このように、ｐＨ１２．５以上の逆抽出剤に逆抽
出されたホウ素の溶解度を、酸を添加することで下げる
ことにより、ホウ素化合物の結晶（Ｎａ2 Ｂ4Ｏ7 ）を
効率的に析出させて回収することができる。4H 3 BO 3 + 2NaOH + 3H 2 O → N
a 2 B 4 O 7 · 10H 2 O In addition, in this way, by lowering by the solubility of boron that is back-extracted to pH12.5 more stripping agents, the addition of acid, crystalline boron compound (Na 2 B 4 O 7 ) can be efficiently precipitated and recovered.
【００１２】本発明によれば、ホウ素を抽出した抽出剤
から、ホウ素を効率的に逆抽出することで、逆抽出後の
抽出剤を再使用して、再生廃液中のホウ素を効率的に抽
出することが可能となる。また、逆抽出剤からホウ素を
効率的に晶析回収することで、ホウ素を晶析除去した後
の逆抽出剤を再使用して、抽出剤の逆抽出をより一層効
率的に行うことが可能となる。According to the present invention, boron is efficiently back-extracted from the boron-extracting extractant, so that the extractant after back-extraction is reused to efficiently extract boron in the regeneration waste liquid. It is possible to do. In addition, by efficiently crystallizing and recovering boron from the back-extracting agent, back-extraction of the extracting agent can be performed even more efficiently by reusing the back-extracting agent after removing the boron by crystallization. Becomes
【００１３】[0013]
【発明の実施の形態】以下に図面を参照して本発明を詳
細に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings.
【００１４】本発明においては、処理対象とするホウ素
含有水は、前述の種々のホウ素利用産業分野から排出さ
れるホウ素含有廃水、原子力発電所から発生する放射性
廃液、地熱発電廃水、排煙脱硫又は脱硝廃水、ゴミ焼却
洗煙廃水、その他各種のホウ素を含有する水であり、こ
れらの水中に、ホウ素は、通常、ＢＯ3 3- の形で含有さ
れている。In the present invention, the boron-containing water to be treated includes boron-containing wastewater discharged from the above-mentioned various fields of boron utilization, radioactive wastewater generated from a nuclear power plant, geothermal power generation wastewater, flue gas desulfurization, and the like. denitrification wastewater, a water containing waste incineration wash smoke wastewater, other various boron, these water boron is normally contained in the BO 3 3- shape.
【００１５】本発明においては、まず、このようなホウ
素含有水をイオン交換樹脂と接触させて処理し、含有さ
れるホウ素を吸着除去する。In the present invention, first, such boron-containing water is treated by bringing it into contact with an ion exchange resin, and the contained boron is absorbed and removed.
【００１６】このイオン交換樹脂による処理は、好まし
くは、弱塩基性アニオン交換樹脂や、Ｎ−（置換）グル
カミン型キレート樹脂を用い、ｐＨ９以上で実施され
る。The treatment with the ion exchange resin is preferably carried out at pH 9 or more using a weakly basic anion exchange resin or an N- (substituted) glucamine type chelate resin.
【００１７】ホウ素含有水を処理したイオン交換樹脂
は、酸と接触させて再生処理する。この再生のための酸
としては、硫酸、塩酸、硝酸等の鉱酸を用いることがで
きる。酸との接触により、イオン交換樹脂に吸着された
ホウ素は溶離し、ホウ素を高濃度で含有する再生廃液が
得られる。一方、酸による処理により、ホウ素を溶離さ
せた樹脂は、必要に応じて水酸化ナトリウム等で処理し
てＯＨ形にした後、再びホウ素含有水の処理に用いるこ
とができる。The ion-exchange resin treated with the boron-containing water is regenerated by bringing it into contact with an acid. Mineral acids such as sulfuric acid, hydrochloric acid and nitric acid can be used as the acid for this regeneration. By contact with the acid, the boron adsorbed on the ion exchange resin is eluted, and a regenerated waste liquid containing a high concentration of boron is obtained. On the other hand, the resin from which boron has been eluted by treatment with an acid can be treated with sodium hydroxide or the like to form an OH form, if necessary, and then used again for treatment of boron-containing water.
【００１８】本発明においては、このようにしてイオン
交換樹脂の再生により得られる再生廃液を、まず、抽出
剤、好ましくは２−エチルヘキサノールを含む抽出剤と
接触させてホウ素を抽出する。使用する抽出剤として
は、２−エチルヘキサノールのみ、又は２−エチルヘキ
サノールにケロシン（燈油）や、その他、ヘプタン、ノ
ナン、デカン、クロロホルム、四塩化炭素、キシレン、
ベンゼン等の抽出溶媒を混合したもの、例えば、ケロシ
ンの場合、２−エチルヘキサノール：ケロシン＝１：
０．１〜２（容量比）で混合して希釈したものを用いる
のが好適である。In the present invention, the regenerated waste liquid thus obtained by regenerating the ion exchange resin is first contacted with an extractant, preferably an extractant containing 2-ethylhexanol, to extract boron. As an extractant to be used, only 2-ethylhexanol or 2-ethylhexanol, kerosene (kerosene), heptane, nonane, decane, chloroform, carbon tetrachloride, xylene,
A mixture of an extraction solvent such as benzene, for example, kerosene, 2-ethylhexanol: kerosine = 1:
It is preferable to use a mixture obtained by mixing and diluting at 0.1 to 2 (volume ratio).
【００１９】この抽出処理により、再生廃液中のホウ素
は極めて高効率で抽出除去されるため、抽残液はそのま
まイオン交換樹脂の再生液として使用することができ
る。By this extraction treatment, the boron in the regenerated waste liquid is extracted and removed with extremely high efficiency, so that the raffinate can be used as it is as a regenerated liquid for the ion exchange resin.
【００２０】次いで、ホウ素を抽出した抽出剤を、ｐＨ
１２．５以上の逆抽出剤と接触させてホウ素を逆抽出す
る。この逆抽出に当り、逆抽出剤のｐＨが１２．５未満
であると、ホウ素を効率的に逆抽出することができな
い。逆抽出剤のｐＨは過度に高いと、後工程の晶析に際
して、ｐＨを下げるための酸の添加量が増大し、また、
逆抽出剤のｐＨが１２．５以上であれば、ｐＨ値の上昇
に対して逆抽出性能が大きく変わることはないため、逆
抽出剤のｐＨは１２．５〜１３．０程度であることが好
ましい。逆抽出剤としては、ＮａＯＨ水溶液、Ｎａ2 Ｃ
Ｏ3 水溶液等のアルカリ水溶液を用いることができる。Next, the extraction agent from which boron was extracted
Back-extract boron by contacting with 12.5 or more back-extracting agent. In this back extraction, if the pH of the back extraction agent is less than 12.5, boron cannot be back-extracted efficiently. If the pH of the back-extracting agent is excessively high, the amount of acid added to lower the pH during crystallization in the subsequent step increases, and
If the pH of the back-extracting agent is 12.5 or more, the back-extracting performance does not greatly change with an increase in the pH value. preferable. NaOH aqueous solution, Na 2 C
An alkaline aqueous solution such as an O 3 aqueous solution can be used.
【００２１】更に、ホウ素を逆抽出した逆抽出剤に酸を
添加して、ホウ素を晶析させる。ここで、再生廃液とし
ては、硫酸、塩酸、硝酸等の鉱酸を用いることができ、
酸添加後の逆抽出剤のｐＨが７〜１２、特に８〜１１と
なるように添加するのが好ましい。酸の添加量が少な
く、酸添加後のｐＨが高いと、ホウ素の溶解度を低くす
ることができず、逆に、酸の添加量が過度に多く、酸添
加後のｐＨが中性付近になると、ホウ素の溶解度が再び
上昇して（Ｎａ2 Ｂ4 Ｏ7 がＨ3 ＢＯ3 となるためと推
定される。）、いずれの場合も晶析効率が十分でなくな
るため、ｐＨを上記範囲に調整することが重要である。Further, an acid is added to the back-extracting agent from which boron has been back-extracted to crystallize boron. Here, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid can be used as the regeneration waste liquid,
It is preferable to add the back-extracting agent so that the pH of the back-extracting agent after the acid addition is 7 to 12, particularly 8 to 11. If the amount of the acid added is small and the pH after the acid addition is high, the solubility of boron cannot be lowered, and conversely, if the amount of the acid added is excessively large and the pH after the acid addition becomes near neutral, , The solubility of boron increases again (presumably because Na 2 B 4 O 7 becomes H 3 BO 3 ), and in any case, the crystallization efficiency becomes insufficient, so that the pH is adjusted to the above range. It is important to.
【００２２】晶析したホウ素化合物の結晶（ホウ酸ナト
リウム）は、これを常法に従って固液分離することによ
り容易に回収することができ、晶析回収したホウ素化合
物は、そのまま、又は、必要に応じて水洗又は熱水に溶
解した後冷却し、再結晶するなどの処理を施して更に純
度を上げた後、各種産業分野のホウ素原料として有効に
利用することができる。一方、ホウ素を除去した後の逆
抽出剤は、アルカリでｐＨ調整することにより、逆抽出
剤として再使用することができる。Crystallized crystals of the boron compound (sodium borate) can be easily recovered by solid-liquid separation according to a conventional method, and the crystallized and recovered boron compound can be used as it is or when necessary. Accordingly, after being subjected to a treatment such as washing with water or dissolving in hot water, cooling, and recrystallization to further increase the purity, it can be effectively used as a boron raw material in various industrial fields. On the other hand, the back extractant from which boron has been removed can be reused as a back extractant by adjusting the pH with an alkali.
【００２３】次に本発明の実施の一例を図１を参照して
更に詳細に説明する。Next, an embodiment of the present invention will be described in more detail with reference to FIG.
【００２４】図１は本発明のホウ素含有水の処理方法の
好適な実施例を示す。１はイオン交換塔、２は抽出塔、
３は逆抽出塔、４はｐＨ調整槽、５は晶析槽である。FIG. 1 shows a preferred embodiment of the method for treating boron-containing water of the present invention. 1 is an ion exchange column, 2 is an extraction column,
3 is a back extraction tower, 4 is a pH adjustment tank, and 5 is a crystallization tank.
【００２５】原水であるホウ素含有水は配管１１よりま
ずイオン交換塔１に送給し、イオン交換樹脂と接触処理
し、処理水は配管１２より系外へ排出する。The boron-containing water, which is raw water, is first sent to the ion exchange tower 1 through a pipe 11 and is subjected to a contact treatment with an ion exchange resin, and the treated water is discharged out of the system through a pipe 12.
【００２６】イオン交換塔１内のイオン交換樹脂がホウ
素で飽和した段階で、原水の供給を停止し、再生液を配
管１３より通液して、イオン交換樹脂に交換吸着された
ホウ素を溶離させる。When the ion exchange resin in the ion exchange tower 1 is saturated with boron, the supply of raw water is stopped, and the regenerated liquid is passed through the pipe 13 to elute the boron exchanged and adsorbed on the ion exchange resin. .
【００２７】再生により生じた再生廃液は配管１４より
抽出塔２内に供給し、配管１５より導入される２−エチ
ルヘキサノールを含む抽出剤と接触させてホウ素を抽出
除去する。抽出により得られる抽残液は配管１６より抜
き出し、必要に応じて配管１７より酸を補給した後、配
管１３を経て再生液としてイオン交換塔１に循環再利用
される。The regenerated waste liquid generated by the regeneration is supplied into the extraction tower 2 from a pipe 14, and brought into contact with an extractant containing 2-ethylhexanol introduced from a pipe 15 to extract and remove boron. The raffinate obtained by the extraction is extracted from the pipe 16 and, if necessary, supplied with an acid from the pipe 17, and then recycled through the pipe 13 as a regenerated liquid to the ion exchange column 1.
【００２８】一方、ホウ素を抽出した抽出剤は、配管１
８より逆抽出塔３に供給し、配管１９より導入される逆
抽出剤と接触させて、ホウ素を逆抽出除去する。逆抽出
によりホウ素を除去した抽出剤は、廃液２０，１５より
抽出塔２に送給され、循環再使用される。On the other hand, the extracting agent from which boron was extracted
8 to the back-extraction tower 3 and contact with the back-extracting agent introduced from the pipe 19 to back-extract and remove boron. The extractant from which boron has been removed by back extraction is sent to the extraction column 2 from the waste liquids 20 and 15, and is recycled and reused.
【００２９】本実施例においては、逆抽出剤として、後
段の晶析槽５でホウ素化合物の結晶を晶析回収した後の
逆抽出剤に、ｐＨ調整槽４において、配管２１よりアル
カリを添加してｐＨ１２．５以上に調整したアルカリ水
溶液を用いる。In this embodiment, an alkali is added from the pipe 21 in the pH adjusting tank 4 to the back extracting agent after the crystals of the boron compound are crystallized and recovered in the subsequent crystallization tank 5 as the back extracting agent. Use an aqueous alkaline solution adjusted to pH 12.5 or more.
【００３０】逆抽出塔３でホウ素を逆抽出した逆抽出剤
は、配管２２より抜き出され、配管２３より酸が添加さ
れて、ｐＨ調整された後、晶析槽５に導入される。晶析
槽５で析出したホウ素化合物の結晶は、配管２４より抜
き出される。一方、逆抽出剤は配管２５よりｐＨ調整槽
４に送給され、前述の如く、ｐＨ調整された後、逆抽出
に循環再使用される。The back-extracting agent from which boron has been back-extracted in the back-extraction tower 3 is extracted from the pipe 22, acid is added from the pipe 23, the pH is adjusted, and then introduced into the crystallization tank 5. Crystals of the boron compound precipitated in the crystallization tank 5 are extracted from the pipe 24. On the other hand, the back-extracting agent is fed from the pipe 25 to the pH-adjusting tank 4 and, as described above, is adjusted for pH and then recycled for back-extraction.
【００３１】[0031]
【実施例】以下に実施例を挙げて本発明をより具体的に
説明する。The present invention will be described more specifically with reference to the following examples.
【００３２】実施例１ ホウ素含有水をＮ−メチルグルカミン型キレート樹脂と
接触させた後、この樹脂を硫酸で再生して、３３００ｍ
ｇ−Ｂ／Ｌ含む再生廃液を得た。この再生廃液を、２−
エチルヘキサノールとケロシンとを１：１の容量比で混
合した抽出剤と、再生廃液：抽出剤＝１：４（容量比）
で接触させて抽出したところ、抽出剤のホウ素濃度は５
８０ｍｇ−Ｂ／Ｌとなった。抽出後の抽出剤を、逆抽出
剤として、表１に示すｐＨのＮａＯＨ水溶液を、表１に
示す割合で用いて逆抽出し、逆抽出率（抽出剤中のホウ
素が逆抽出剤中に逆抽出される割合：逆抽出率１００％
であれば、抽出剤中のホウ素濃度は０となる。）を調
べ、結果を表１に示した。Example 1 After bringing boron-containing water into contact with an N-methylglucamine-type chelating resin, the resin was regenerated with sulfuric acid to obtain 3300 m
A regeneration waste liquid containing g-B / L was obtained. This reclaimed waste liquid is
An extractant obtained by mixing ethylhexanol and kerosene at a volume ratio of 1: 1 and a regeneration waste liquid: extractant = 1: 4 (volume ratio)
Extraction, the boron concentration of the extractant was 5
It became 80 mg-B / L. The extraction agent after the extraction is used as a back-extracting agent and back-extracted using an aqueous NaOH solution having the pH shown in Table 1 at a ratio shown in Table 1, and the back-extraction rate (boron in the back-extracting agent Extraction rate: 100% back extraction rate
If so, the boron concentration in the extractant becomes zero. ) And the results are shown in Table 1.
【００３３】表１より、ｐＨ１２．５以上の逆抽出剤で
あれば、ホウ素を効率的に逆抽出できることが明らかで
ある。From Table 1, it is clear that a back-extracting agent having a pH of 12.5 or more can efficiently back-extract boron.
【００３４】[0034]
【表１】 [Table 1]
【００３５】実施例２ ミキサー部容量３Ｌ、セトラー部容量２４Ｌの抽出塔を
５塔直列に設置し、ホウ素を４０００ｍｇ／Ｌ含有する
イオン交換樹脂の再生廃液を１０．５Ｌ／ｈｒで供給す
ると共に、実施例１で用いたものと同様の抽出剤を４２
Ｌ／ｈｒで供給してホウ素の抽出を行った。Example 2 Five extraction towers each having a mixer volume of 3 L and a settler volume of 24 L were installed in series, and a regenerated wastewater of ion exchange resin containing 4000 mg / L of boron was supplied at 10.5 L / hr. An extractant similar to that used in Example 1 was added to 42
L / hr was supplied to extract boron.
【００３６】逆抽出塔として上記と同様の抽出塔を１塔
用いて、ホウ素を抽出した抽出剤を４２Ｌ／ｈｒで供給
すると共に、逆抽出剤としてｐＨ１３のＮａＯＨ水溶液
を１０．５Ｌ／ｈｒで供給して逆抽出を行い、逆抽出後
の抽出剤を前記抽出工程に循環使用した。Using one extraction tower similar to the above as a back extraction tower, an extractant from which boron was extracted was supplied at 42 L / hr, and a pH 13 NaOH aqueous solution was supplied at 10.5 L / hr as a back extraction agent. Then, the back extraction was performed, and the extractant after back extraction was circulated and used in the extraction step.
【００３７】更に、逆抽出後の逆抽出剤に硫酸を添加し
てｐＨ９．７に調整して晶析を行った。その後、晶析後
の逆抽出剤にＮａＯＨを加えてｐＨ１３．０に調整し、
再度、上記と同様の逆抽出に使用した。Further, sulfuric acid was added to the back extraction agent after back extraction to adjust the pH to 9.7, and crystallization was carried out. Thereafter, NaOH was added to the back extractant after crystallization to adjust the pH to 13.0,
Again, it was used for back extraction as above.
【００３８】抽出塔出口の再生廃液のホウ素濃度、逆抽
出塔出口の逆抽出剤のホウ素濃度、晶析槽出口の逆抽出
剤のホウ素濃度をそれぞれ調べ、結果を表２に示した。The boron concentration of the regenerated waste liquid at the outlet of the extraction tower, the boron concentration of the back extractant at the outlet of the back extraction tower, and the boron concentration of the back extractant at the outlet of the crystallization tank were examined. The results are shown in Table 2.
【００３９】比較のため、逆抽出後の逆抽出剤に硫酸を
添加しなかったこと以外は上記と同様に行った。その結
果、経時により、逆抽出塔にホウ酸ナトリウムの結晶が
析出し、撹拌機のスケールトラブルで運転を継続するこ
とが不可能となった。定常運転時の各部のホウ素濃度
は、表２に示す通りであり、抽出、逆抽出及び晶析の効
率はいずれも本発明例に比べて著しく劣るものであっ
た。For comparison, the procedure was the same as above except that sulfuric acid was not added to the back extraction agent after back extraction. As a result, as time passed, sodium borate crystals precipitated in the back extraction tower, and it became impossible to continue the operation due to scale trouble of the stirrer. The boron concentration of each part at the time of steady operation was as shown in Table 2, and the extraction, back extraction and crystallization efficiencies were all significantly inferior to those of the inventive examples.
【００４０】[0040]
【表２】 [Table 2]
【００４１】実施例３ 実施例２の逆抽出塔出口の逆抽出剤（ホウ素を１１１０
０ｍｇ／Ｌ含むＮａＯＨ水溶液）に硫酸を添加して表３
に示すｐＨに調整し、結晶の析出量を調べ、結果を表３
に示した。Example 3 The back extraction agent at the outlet of the back extraction column in Example 2 (boron was added to 1110
0 mg / L aqueous solution of NaOH) and sulfuric acid.
Was adjusted to the pH shown in Table 3, and the amount of precipitated crystals was examined.
It was shown to.
【００４２】表３より、酸を添加して好ましくはｐＨ７
〜１２，より好ましくはｐＨ８〜１１に調整することに
より、晶析効率が向上することがわかる。According to Table 3, it is preferable to add an acid,
It can be seen that the crystallization efficiency is improved by adjusting the pH to 12 or more, more preferably 8 to 11.
【００４３】[0043]
【表３】 [Table 3]
【００４４】[0044]
【発明の効果】以上詳述した通り、本発明のホウ素含有
水の処理方法によれば、ホウ素含有水をイオン交換樹脂
と接触させて処理した後のイオン交換樹脂の再生廃液か
ら、ホウ素を効率的に抽出すると共に、ホウ素を抽出し
た抽出剤からホウ素を効率的に逆抽出し、更に、ホウ素
を逆抽出した逆抽出剤から、ホウ素を効率的に晶析回収
することができる。As described above in detail, according to the method for treating boron-containing water of the present invention, boron can be efficiently removed from the waste water of regenerated ion-exchange resin after the treatment by contacting the boron-containing water with the ion-exchange resin. In addition to efficient extraction, boron can be efficiently back-extracted from the boron-extracting extractant, and boron can be efficiently crystallized and recovered from the back-extractant from which boron has been back-extracted.
【００４５】このため、本発明によれば、再生廃液、抽
出剤、逆抽出剤及び晶析回収したホウ素化合物を各々有
効に再利用することが可能となる。Therefore, according to the present invention, it is possible to effectively reuse the recycled waste liquid, the extractant, the back-extractant, and the boron compound recovered by crystallization.
【図１】本発明のホウ素含有水の処理方法の一実施例方
法を示す系統図である。FIG. 1 is a system diagram showing one embodiment of a method for treating boron-containing water according to the present invention.
１ イオン交換塔 ２ 抽出塔 ３ 逆抽出塔 ４ ｐＨ調整槽 ５ 晶析槽 DESCRIPTION OF SYMBOLS 1 Ion exchange tower 2 Extraction tower 3 Back extraction tower 4 pH adjustment tank 5 Crystallization tank
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岡 淳雄 大阪市北区中之島３丁目３番22号 関西 電力株式会社内 (72)発明者 砥山 浩司 大阪市北区中之島３丁目３番22号 関西 電力株式会社内 (72)発明者 白方 正 東京都中央区銀座６丁目15番１号 電源 開発株式会社内 (72)発明者 春名 恭年 東京都中央区銀座６丁目15番１号 電源 開発株式会社内 (72)発明者 武藤 憲一 東京都中央区銀座６丁目15番１号 電源 開発株式会社内 (72)発明者 恵藤 良弘 東京都新宿区西新宿３丁目４番７号 栗 田工業株式会社内 (72)発明者 山田 亮一 東京都新宿区西新宿３丁目４番７号 栗 田工業株式会社内 (72)発明者 朝田 裕之 東京都新宿区西新宿３丁目４番７号 栗 田工業株式会社内 (72)発明者 堀井 重希 東京都新宿区西新宿３丁目４番７号 栗 田工業株式会社内 (56)参考文献 特公 平１−50476（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) C02F 1/26 C01F 1/42 B01D 11/00 - 12/00 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Atsushi Oka 3-3-22 Nakanoshima, Kita-ku, Osaka City Kansai Electric Power Co., Inc. (72) Inventor Koji Toyama 3-3-22 Nakanoshima, Kita-ku, Osaka Kansai Electric Power (72) Inventor Tadashi Shirakata 6-15-1, Ginza, Chuo-ku, Tokyo Power Supply Development Co., Ltd. (72) Inventor Yasunori Haruna 6-15-1, Ginza, Chuo-ku, Tokyo Power Supply Development Co., Ltd. (72) Inventor Kenichi Muto 6-15-1, Ginza, Chuo-ku, Tokyo Inside Power Development Co., Ltd. (72) Inventor Yoshihiro Keito 3-4-7 Nishi-Shinjuku, Shinjuku-ku, Tokyo Kurita Water Industries Co., Ltd. (72) Inventor Ryoichi Yamada 3-4-7 Nishi Shinjuku, Shinjuku-ku, Tokyo Inside Kurita Kogyo Co., Ltd. (72) Inventor Hiroyuki Asada 3-4-7 Nishi-Shinjuku, Shinjuku-ku, Tokyo Kurita Kogyo Co., Ltd. (72) Inventor Shigeki Horii 3-4-7 Nishi-Shinjuku, Shinjuku-ku, Tokyo Inside Kurita Water Industries Ltd. (56) References JP-B-1-50476 (JP, B2) (58) Field (Int.Cl. 7 , DB name) C02F 1/26 C01F 1/42 B01D 11/00-12/00
Claims (2)
せた後、該イオン交換樹脂を酸と接触させて再生し、こ
の再生廃液を抽出剤と接触させてホウ素を抽出した後、
ホウ素を抽出した抽出剤を逆抽出剤と接触させてホウ素
を逆抽出するホウ素含有水の処理方法において、 前記逆抽出剤としてｐＨ１２．５以上の逆抽出剤を用い
ることを特徴とするホウ素含有水の処理方法。After contacting the boron-containing water with the ion-exchange resin, the ion-exchange resin is regenerated by contacting with an acid, and the regenerated waste liquid is contacted with an extractant to extract boron.
A method for treating boron-containing water, wherein the boron-extracting agent is brought into contact with a back-extracting agent to back-extract boron, wherein a back-extracting agent having a pH of 12.5 or more is used as the back-extracting agent. Processing method.
出した逆抽出剤に酸を添加してホウ素を晶析させること
を特徴とするホウ素含有水の処理方法。2. The method for treating boron-containing water according to claim 1, wherein an acid is added to the back-extracting agent obtained by back-extracting boron to crystallize boron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13360696A JP3336858B2 (en) | 1996-05-28 | 1996-05-28 | Method for treating boron-containing water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13360696A JP3336858B2 (en) | 1996-05-28 | 1996-05-28 | Method for treating boron-containing water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09314130A JPH09314130A (en) | 1997-12-09 |
| JP3336858B2 true JP3336858B2 (en) | 2002-10-21 |
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ID=15108741
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13360696A Expired - Fee Related JP3336858B2 (en) | 1996-05-28 | 1996-05-28 | Method for treating boron-containing water |
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| JP4615234B2 (en) * | 2004-03-30 | 2011-01-19 | 独立行政法人科学技術振興機構 | Method for insolubilizing and separating boron dissolved in water, method for detoxifying boron dissolved wastewater, and method for recovering boron resources |
| JP4825858B2 (en) * | 2008-09-17 | 2011-11-30 | 株式会社東芝 | Boron separation system |
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1996
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| Publication number | Publication date |
|---|---|
| JPH09314130A (en) | 1997-12-09 |
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