JP2000176438A - Extraction method - Google Patents
Extraction methodInfo
- Publication number
- JP2000176438A JP2000176438A JP10361088A JP36108898A JP2000176438A JP 2000176438 A JP2000176438 A JP 2000176438A JP 10361088 A JP10361088 A JP 10361088A JP 36108898 A JP36108898 A JP 36108898A JP 2000176438 A JP2000176438 A JP 2000176438A
- Authority
- JP
- Japan
- Prior art keywords
- extraction
- agent
- boron
- extractant
- back extraction
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、抽出操作と逆抽出
操作とを有する抽出方法に関する。詳しくは、抽出部に
おいて被処理水を抽出剤と接触させて該被処理水中のホ
ウ素等の目的物質を該抽出剤中に抽出した後、逆抽出部
において該目的物質を抽出した抽出剤を逆抽出剤と接触
させて該目的物質を該逆抽出剤中に逆抽出し、さらに該
逆抽出剤中の該目的物質を晶析させて回収する抽出方法
に係り、特に、この抽出方法において、逆抽出前後の逆
抽出剤のｐＨを適正に制御することにより、抽出、逆抽
出及び晶析回収までを効率的に行えるようにした抽出方
法に関する。[0001] The present invention relates to an extraction method having an extraction operation and a back extraction operation. Specifically, after the water to be treated is brought into contact with the extractant in the extraction section to extract a target substance such as boron in the water to be treated into the extractant, the extractant from which the target substance is extracted in the reverse extraction section is reversely extracted. The present invention relates to an extraction method in which the target substance is back-extracted into the back-extracting agent by contact with an extracting agent, and the target substance in the back-extracting agent is crystallized and recovered. The present invention relates to an extraction method in which extraction, back-extraction, and crystallization recovery can be efficiently performed by appropriately controlling the pH of a back-extraction agent before and after extraction.
【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（Ｎａ2ＣＯ3）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して回収する。
そして、逆抽出処理後の抽出剤及び晶析処理後の逆抽出
剤はそれぞれ循環再使用し、不足分のみを系内に補給す
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.
Then, the extractant after the back extraction treatment and the back extraction agent after the crystallization treatment are respectively circulated and reused, and only the shortage is supplied into the system.
【０００５】また、このような方法において、逆抽出条
件及び晶析条件を最適化したものとして、特開平９−３
１４１３０号公報には、ホウ素を含む抽出剤を接触させ
る逆抽出前の逆抽出剤のｐＨを１２．５以上として逆抽
出効率を高め、更に逆抽出剤中のホウ素を晶析により分
離する際に、逆抽出後の逆抽出剤に酸を加えて晶析効率
を向上させる方法が提案されている。[0005] Further, in such a method, the back extraction conditions and the crystallization conditions are optimized as disclosed in
No. 14130 discloses that the pH of a back-extracting agent before back-extraction, which is brought into contact with an extracting agent containing boron, is 12.5 or more to increase the back-extraction efficiency, and further, when boron in the back-extracting agent is separated by crystallization. There has been proposed a method of improving the crystallization efficiency by adding an acid to the back extraction agent after back extraction.
【０００６】即ち、このようなホウ素の逆抽出及び晶析
処理においては、ｐＨ条件は極めて重要な因子であり、
逆抽出前の逆抽出剤のｐＨは高い程、逆抽出効率は向上
し、また、逆抽出後の逆抽出剤からのホウ素の晶析に際
しては、ｐＨを下げた方が晶析効率が向上する。That is, in such back extraction and crystallization of boron, the pH condition is a very important factor.
The higher the pH of the back extraction agent before back extraction, the higher the back extraction efficiency, and the lower the pH, the higher the crystallization efficiency in boron crystallization from the back extraction agent after back extraction. .
【０００７】これは、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、逆抽出剤のアルカリ濃度が高い程
向上するためと推定される。[0007] This is because the back-extraction mechanism consists of the reaction of boric acid in the extractant with the alkali in the back-extractant as shown in the following formula. The back-extraction efficiency increases as the alkali concentration of the back-extractant increases. It is estimated to improve.
【０００８】 ４Ｈ3ＢＯ3＋２ＮａＯＨ→Ｎａ2Ｂ4Ｏ7＋７Ｈ2Ｏ また、このように、高ｐＨ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（Ｎａ2Ｂ4Ｏ7）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 → Na 2 B 4 O 7 + 7H 2 O Further, by lowering the solubility of boron back-extracted with a high-pH back-extracting agent by adding an acid, The boron compound crystals (Na 2 B 4 O 7 ) can be efficiently precipitated and recovered.
【０００９】[0009]
【発明が解決しようとする課題】しかしながら、このよ
うに逆抽出前の逆抽出剤のｐＨを最適ｐＨ値に調整して
逆抽出を行っても、被抽出物（原水）のホウ素濃度が変
動し、これにより抽出剤のホウ素濃度が変動した場合に
は、逆抽出後の逆抽出剤のｐＨが変動することとなるた
め、特開平９−３１４１３０号公報記載の方法では常に
最適なｐＨ条件を維持することはできず、逆抽出効率及
び晶析効率が低下する場合がある。However, even if the pH of the back extraction agent before back extraction is adjusted to the optimum pH value and back extraction is performed, the boron concentration of the extract (raw water) fluctuates. If the boron concentration of the extractant fluctuates, the pH of the back-extractant after back-extraction will fluctuate. Therefore, the method described in JP-A-9-314130 always maintains the optimum pH condition. And the back extraction efficiency and the crystallization efficiency may decrease.
【００１０】即ち、前述の反応式でホウ酸とアルカリが
反応するとアルカリの消費で逆抽出後の逆抽出剤のｐＨ
は低下するが、例えば、抽出剤のホウ素濃度が平常時よ
りも低くなった場合には、逆抽出されるホウ素量が少な
いことから、この逆抽出剤のｐＨの低下幅が小さいため
に逆抽出後の逆抽出剤のｐＨは平常時よりも高くなる。
このような高ｐＨの逆抽出剤では、晶析が起こり難く、
ホウ素化合物結晶の溶解が起こる。逆に、抽出剤のホウ
素濃度が平常時よりも高くなった場合には、逆抽出され
るホウ素量が多いことから、逆抽出による逆抽出剤のｐ
Ｈの低下幅が平常時よりも大きくなるために、逆抽出後
の逆抽出剤のｐＨが低くなる。この場合には、逆抽出が
不完全となり、抽出剤中にホウ素が残留する。That is, when boric acid reacts with an alkali in the above-mentioned reaction formula, the pH of the back-extracting agent after back-extraction is reduced by consumption of the alkali.
For example, when the boron concentration of the extractant is lower than normal, the amount of boron to be back-extracted is small. The pH of the later back-extractant will be higher than normal.
With such a high pH back-extracting agent, crystallization hardly occurs,
Dissolution of the boron compound crystals occurs. Conversely, when the boron concentration of the extractant is higher than normal, the amount of boron to be back-extracted is large.
Since the decrease width of H is larger than usual, the pH of the back extraction agent after back extraction is lowered. In this case, the back extraction is incomplete and boron remains in the extractant.
【００１１】抽出剤のホウ素濃度が低くなった場合の晶
析不良は、特開平９−３１４１３０号公報記載の方法に
おいて、逆抽出後の逆抽出剤に添加する酸の添加量を増
加させることで対応することはできる。しかしながら、
抽出剤のホウ素濃度が高くなった場合の逆抽出不良には
対応し得ず、この場合には、循環使用される抽出剤中の
残留ホウ素濃度が高くなることにより抽出効率も低下
し、また、逆抽出剤のｐＨが低下することで、逆抽出剤
中でホウ酸ナトリウムのスケールが析出するなどの不具
合も生じる。[0011] Crystallization failure when the boron concentration of the extractant becomes low can be caused by increasing the amount of acid added to the back-extracting agent after back-extraction in the method described in JP-A-9-314130. Yes, you can. However,
It is impossible to cope with poor back extraction when the boron concentration of the extractant is high, and in this case, the extraction efficiency is reduced due to the increase in the residual boron concentration in the extractant used in circulation, and When the pH of the back-extracting agent decreases, problems such as precipitation of sodium borate scale in the back-extracting agent also occur.
【００１２】本発明は上記従来の問題点を解決し、抽出
部において被処理水を抽出剤と接触させて該被処理水中
のホウ素等の目的物質を該抽出剤中に抽出した後、逆抽
出部において該目的物質を抽出した抽出剤を逆抽出剤と
接触させて該目的物質を該逆抽出剤中に逆抽出し、さら
に該逆抽出剤中の該目的物質を晶析させて回収する抽出
方法において、逆抽出前後の逆抽出剤のｐＨを適正に制
御することにより、負荷変動、即ち、被処理水中の目的
物質濃度の変動に十分対応して抽出、逆抽出及び晶析回
収までの一連の処理を安定かつ効率的に行うことができ
る抽出方法を提供することを目的とする。[0012] The present invention solves the above-mentioned conventional problems. In the extraction section, the water to be treated is brought into contact with an extractant to extract a target substance such as boron in the water to be treated into the extractant, and then back-extracted. The extractant in which the target substance is extracted in the section is brought into contact with a back-extracting agent to back-extract the target substance into the back-extracting agent, and further, the target substance in the back-extracting agent is crystallized and recovered. In the method, by appropriately controlling the pH of the back-extraction agent before and after back-extraction, load fluctuation, that is, a series of steps from extraction, back-extraction and crystallization recovery in sufficient response to the fluctuation of the target substance concentration in the water to be treated. It is an object of the present invention to provide an extraction method capable of performing the processing in a stable and efficient manner.
【００１３】[0013]
【課題を解決するための手段】本発明の抽出方法は、抽
出部において被処理水を抽出剤と接触させて該被処理水
中の目的物質を該抽出剤中に抽出した後、逆抽出部にお
いて該目的物質を抽出した抽出剤を逆抽出剤と接触させ
て該目的物質を該逆抽出剤中に逆抽出し、更に該逆抽出
剤中の該目的物質を晶析させて回収する抽出方法におい
て、逆抽出後の逆抽出剤のｐＨ値に基いて、逆抽出前の
逆抽出剤のｐＨ値を調整することを特徴とする。According to the extraction method of the present invention, the water to be treated is brought into contact with the extractant in the extraction section to extract the target substance in the water to be extracted into the extractant, and then the extraction is carried out in the back extraction section. In an extraction method, the extractant from which the target substance has been extracted is brought into contact with a back-extractant to back-extract the target substance into the back-extractant, and further, the target substance in the back-extractant is crystallized and recovered. The method is characterized in that the pH value of the back extraction agent before back extraction is adjusted based on the pH value of the back extraction agent after back extraction.
【００１４】本発明方法に従って、抽出剤と接触した後
の逆抽出剤のｐＨを測定し、その値に応じて逆抽出部に
供給する逆抽出前の逆抽出剤のｐＨを調整することによ
り、逆抽出後の逆抽出剤のｐＨを適正な値に維持するこ
とができる。According to the method of the present invention, the pH of the back extraction agent after contact with the extraction agent is measured, and the pH of the back extraction agent to be supplied to the back extraction unit before back extraction is adjusted according to the measured value. The pH of the back extraction agent after back extraction can be maintained at an appropriate value.
【００１５】即ち、逆抽出後の逆抽出剤のｐＨが予め定
めたｐＨよりも低い場合には、抽出剤中のホウ素濃度が
高いためであるから、逆抽出部に供給する逆抽出前の逆
抽出剤のｐＨを上げ、逆抽出後の逆抽出剤のｐＨの低下
及びこれによる逆抽出不良を防止する。逆に、この逆抽
出後の逆抽出剤のｐＨが予め定めたｐＨよりも高い場合
には、抽出剤中のホウ素濃度が低いためであるから、逆
抽出部に供給する逆抽出前の逆抽出剤のｐＨを下げ、逆
抽出後の逆抽出剤のｐＨの上昇及びこれによるスケール
析出を防止する。That is, when the pH of the back extraction agent after back extraction is lower than a predetermined pH, the concentration of boron in the back extraction agent is high. By increasing the pH of the extractant, it is possible to prevent a decrease in the pH of the backextractor after the backextraction, and to prevent poor backextraction due to this. Conversely, if the pH of the back extraction agent after the back extraction is higher than a predetermined pH, it is because the boron concentration in the extraction agent is low, so the back extraction before back extraction to be supplied to the back extraction unit The pH of the agent is lowered to prevent an increase in the pH of the back-extracting agent after back-extraction and thereby scale deposition.
【００１６】このようにして、抽出剤中のホウ素濃度の
変動に対して逆抽出後のｐＨを一定に保つように逆抽出
前の逆抽出剤のｐＨを調整することにより、逆抽出性能
及び晶析性能を安定させることができる。In this way, by adjusting the pH of the back extraction agent before back extraction so that the pH after back extraction is kept constant with respect to the fluctuation of the boron concentration in the extraction agent, the back extraction performance and crystal The analysis performance can be stabilized.
【００１７】本発明において、逆抽出前の逆抽出剤のｐ
Ｈ調整は、ｐＨ調整剤の添加量制御により容易に行うこ
とができる。この逆抽出剤へのｐＨ調整剤の添加はｐＨ
調整槽を設けて行っても良く、逆抽出剤槽に対して直接
行っても良い。In the present invention, p of the back-extracting agent before back-extraction is used.
H adjustment can be easily performed by controlling the addition amount of the pH adjuster. The addition of a pH adjuster to this back-extract
It may be performed by providing an adjustment tank, or may be directly performed on the back extraction agent tank.
【００１８】[0018]
【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.
【００１９】図１は本発明の抽出方法の実施の形態を示
すホウ素の逆抽出及び晶析プロセスの系統図であり、１
は逆抽出剤槽、２はｐＨ調整槽、３は逆抽出塔、４は晶
析槽である。FIG. 1 is a system diagram of a boron back extraction and crystallization process showing an embodiment of the extraction method of the present invention.
Denotes a back extraction agent tank, 2 denotes a pH adjustment tank, 3 denotes a back extraction tower, and 4 denotes a crystallization tank.
【００２０】抽出塔（図示せず）で被処理水と接触し、
被処理水中のホウ素を抽出して含む抽出剤は、逆抽出塔
３に供給され、逆抽出剤と撹拌接触され、ホウ素が逆抽
出除去される。逆抽出によりホウ素を除去した抽出剤
は、抽出塔に戻され、循環再使用される。Contacting the water to be treated in an extraction tower (not shown),
The extractant containing boron extracted from the water to be treated is supplied to the back-extraction tower 3 and is brought into contact with the back-extractant by stirring to back-extract and remove boron. The extracting agent from which boron has been removed by back extraction is returned to the extraction column and recycled.
【００２１】この逆抽出塔３に供給する逆抽出剤として
は、後述の晶析槽４でホウ素化合物の結晶を晶析回収し
た後の逆抽出剤に、アルカリを添加して適当なｐＨに調
整したものが用いられる。The back-extracting agent supplied to the back-extraction column 3 is adjusted to an appropriate pH by adding an alkali to the back-extracting agent after crystallizing and recovering the boron compound crystals in the crystallization tank 4 described below. Is used.
【００２２】即ち、図１において、晶析槽４から返送さ
れた逆抽出剤は、逆抽出槽１を経てポンプＰ1によりｐ
Ｈ調整槽２に導入され、このｐＨ調整槽２において、逆
抽出塔３から晶析槽４に逆抽出剤を送給する配管に設け
られたｐＨ計４Ａと、ｐＨ調整槽２に設けられたｐＨ計
２Ａとに連動する薬注ポンプＰ2によりアルカリが添加
され、ｐＨ調整が行われる。That is, in FIG. 1, the back extractant returned from the crystallization tank 4 passes through the back extraction tank 1 and is pumped by the pump P 1.
The pH adjusting tank 2 was introduced into the H adjusting tank 2. In the pH adjusting tank 2, a pH meter 4 </ b> A was provided in a pipe for feeding a back extraction agent from the back extraction tower 3 to the crystallization tank 4, and provided in the pH adjusting tank 2. alkali is added by chemical feed pump P 2 interlocked with a pH meter 2A, pH adjustment is performed.
【００２３】ホウ素の逆抽出において、逆抽出剤として
は、ＮａＯＨ水溶液、Ｎａ2ＣＯ3水溶液等のアルカリ水
溶液が用いられ、一般的には、この逆抽出剤の逆抽出前
のｐＨは１２．５以上に調整される。逆抽出前の逆抽出
剤の調整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、逆抽出剤の逆抽出前のｐＨ
は１２．５〜１３．５の範囲で、逆抽出後の逆抽出剤の
ｐＨに基いて調整するのが好ましい。In the back extraction of boron, an alkaline aqueous solution such as an aqueous NaOH solution or an aqueous solution of Na 2 CO 3 is used as the back extraction agent. Generally, the pH of the back extraction agent before back extraction is 12.5. It is adjusted above. If the adjusted pH of the back extraction agent before back extraction is less than 12.5, boron cannot be back extracted efficiently. The pH of the back extractant is 12.
If the pH is 5 or more, the back extraction performance does not change significantly with an increase in the pH value.
Is preferably in the range of 12.5 to 13.5 and adjusted based on the pH of the back extraction agent after back extraction.
【００２４】なお、逆抽出温度は２０℃以上の範囲でよ
い。The back extraction temperature may be in the range of 20 ° C. or higher.
【００２５】ｐＨ調整槽２からポンプＰ３により逆抽出
塔３に供給され、逆抽出塔３でホウ素を逆抽出した逆抽
出剤は、晶析槽４に導入され、好ましくは逆抽出温度よ
りも５℃以上低い温度で晶析処理される。晶析槽４で析
出したホウ素化合物（ホウ酸ナトリウム）の結晶は、晶
析槽４の底部より抜き出され、そのまま、或いは、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再利用される。The back-extracting agent supplied from the pH adjusting tank 2 to the back-extraction column 3 by the pump P3 and back-extracting the boron in the back-extraction column 3 is introduced into the crystallization tank 4, and is preferably at a temperature lower than the back-extraction temperature by 5 ° C. The crystallization is performed at a temperature lower than ℃. Crystals of the boron compound (sodium borate) precipitated in the crystallization tank 4 are extracted from the bottom of the crystallization tank 4 and cooled as it is, or, if necessary, washed with water or dissolved in hot water, and then recrystallized. After further increasing the purity by performing such treatments, the material is effectively reused as a boron raw material in various industrial fields.
【００２６】一方、逆抽出剤は逆抽出剤槽１に返送さ
れ、ｐＨ調整槽２でｐＨ調整された後、逆抽出に循環再
使用される。On the other hand, the back extraction agent is returned to the back extraction agent tank 1 and adjusted in pH in the pH adjustment tank 2, and then recycled and used for back extraction.
【００２７】本発明では、このような逆抽出、晶析処理
に当り、逆抽出後の逆抽出剤のｐＨを測定し、この測定
値に基いて、逆抽出塔３に供給される逆抽出剤のｐＨを
制御する。即ち、図１においては、逆抽出塔３でホウ素
を逆抽出した逆抽出剤を晶析槽４へ送給する配管にｐＨ
計４Ａを設けてｐＨ測定を行い、この結果に基いて、逆
抽出後の逆抽出剤のｐＨが予め定めた設定ｐＨ値となる
ように、逆抽出前の逆抽出剤のｐＨ値が決定され、この
結果に基づいて薬注ポンプＰ2の作動が制御され、ｐＨ
調整槽２へのアルカリ添加量が調整される逆抽出後の逆
抽出剤のｐＨが予め定めた設定ｐＨ値よりも低い場合
は、抽出剤中のホウ素濃度が高いのであるから、逆抽出
剤のｐＨを上げるべくｐＨ調整槽２へのアルカリの供給
量を増やす。逆に、逆抽出後の逆抽出剤のｐＨが予め定
めた設定ｐＨ値よりも高い場合は、抽出剤中のホウ素濃
度が低いのであるから、逆抽出剤のｐＨを下げるべくｐ
Ｈ調整槽２へのアルカリの供給量を減らす。In the present invention, in such back extraction and crystallization treatment, the pH of the back extraction agent after back extraction is measured, and based on the measured value, the back extraction agent supplied to the back extraction tower 3 is measured. To control the pH. That is, in FIG.
The pH value of the back-extracting agent before back-extraction is determined on the basis of the result by measuring the pH of the back-extracting agent before back-extraction so that the back-extraction agent has a predetermined set pH value. the result operation of chemical feed pump P 2 based on is controlled, pH
When the pH of the back extraction agent after back extraction in which the amount of alkali added to the adjustment tank 2 is adjusted is lower than a predetermined set pH value, the boron concentration in the extraction agent is high, The supply amount of alkali to the pH adjusting tank 2 is increased to increase the pH. Conversely, when the pH of the back extraction agent after back extraction is higher than a predetermined set pH value, the boron concentration in the back extraction agent is low, and therefore, p is set to lower the pH of the back extraction agent.
The supply amount of alkali to the H adjustment tank 2 is reduced.
【００２８】このように、逆抽出後の逆抽出剤のｐＨ測
定値に基いて逆抽出剤へのアルカリの供給量を増減して
逆抽出前の逆抽出剤のｐＨを調整することにより、逆抽
出後の逆抽出剤のｐＨを適正なｐＨ値（設定ｐＨ値）に
維持することができるようになり、逆抽出系内のｐＨを
維持して効率的な逆抽出を行うことができるようにな
る。また、このように逆抽出後のｐＨの安定した逆抽出
剤であれば、晶析槽４において、結晶の溶解等を起こす
ことなく効率的な晶析を行える。As described above, by adjusting the pH of the back-extracting agent before back-extraction by increasing or decreasing the supply amount of alkali to the back-extracting agent based on the pH value of the back-extracting agent after back-extraction. It is possible to maintain the pH of the back extraction agent after extraction at an appropriate pH value (set pH value), and to maintain the pH in the back extraction system so that efficient back extraction can be performed. Become. In addition, if the back extraction agent has a stable pH after back extraction, efficient crystallization can be performed in the crystallization tank 4 without dissolving the crystals.
【００２９】本発明において、逆抽出後の逆抽出剤の設
定ｐＨ値は、効率的な逆抽出及び晶析が行えるようなｐ
Ｈ値であれば良く、特に制限はないが、通常の場合、１
２．０〜１２．６程度に設定される。In the present invention, the set pH value of the back-extracting agent after back-extraction is determined so that efficient back-extraction and crystallization can be performed.
There is no particular limitation as long as it is an H value.
It is set to about 2.0 to 12.6.
【００３０】このような設定ｐＨ値に対する測定ｐＨ値
に基く逆抽出前の逆抽出剤のｐＨ値の制御基準は、予め
計算又は実験等で求めておけば良く、例えば、逆抽出前
の逆抽出剤（ホウ素濃度約２２０００ｍｇ／Ｌ）のｐＨ
とホウ素を逆抽出した後の逆抽出剤のｐＨについては、
図２に示すような関係であり、このようなグラフに基い
て後述の実験例１に示す方法によりｐＨ調整を行うこと
ができる。The control criterion for the pH value of the back-extracting agent before back-extraction based on the measured pH value with respect to the set pH value may be obtained in advance by calculation or experiment, for example, back-extraction before back-extraction. PH of the agent (boron concentration about 22000mg / L)
And the pH of the back-extraction agent after back-extraction of boron,
The relationship is as shown in FIG. 2, and the pH can be adjusted based on such a graph by the method shown in Experimental Example 1 described later.
【００３１】なお、図１において、ｐＨ調整槽２は必ず
しも必要とされず、逆抽出槽１に直接アルカリを添加し
てｐＨ調整を行っても良い。また、逆抽出後の逆抽出剤
のｐＨの測定は、晶析槽４又は晶析槽４から逆抽出剤槽
１へ逆抽出剤を返送する配管にｐＨ計を設けて行っても
よく、逆抽出前の逆抽出剤のｐＨの測定は逆抽出塔３へ
逆抽出剤を供給する配管にｐＨ計を設けて行っても良
い。In FIG. 1, the pH adjustment tank 2 is not always required, and the pH may be adjusted by directly adding an alkali to the back extraction tank 1. The pH of the back extraction agent after back extraction may be measured by providing a pH meter in the crystallization tank 4 or in a pipe for returning the back extraction agent from the crystallization tank 4 to the back extraction agent tank 1. The pH of the back extraction agent before the extraction may be measured by providing a pH meter in a pipe for supplying the back extraction agent to the back extraction column 3.
【００３２】本実施の形態において、処理対象とするホ
ウ素を含む抽出剤とは、例えば、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
（通常、ＢＯ3 3-の形で含有されている。）を含有する
水を、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とｐＨ９以上で接触させて処理し、
含有されるホウ素を吸着除去した後、このホウ素を吸着
したイオン交換樹脂を硫酸、塩酸、硝酸等の鉱酸と接触
させて再生処理して得られる再生廃液を抽出処理して得
られるものである。この抽出剤としては、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 embodiment, the extraction agent containing boron to be treated includes, for example, boron-containing wastewater discharged from the above-mentioned various boron utilization industries, radioactive wastewater generated from a nuclear power plant, geothermal power generation. wastewater, flue gas desulfurization or denitration wastewater, waste incineration wash smoke wastewater, other various boron (usually contained. in BO 3 3- shape) water containing, and weakly basic anion exchange resins N- (Substituted) contact with a glucamine-type chelate resin at pH 9 or more,
After adsorbing and removing the contained boron, the ion-exchange resin adsorbing the boron is brought into contact with a mineral acid such as sulfuric acid, hydrochloric acid, nitric acid or the like to be subjected to a regenerating treatment, and a reclaimed waste liquid obtained by extraction treatment is obtained. . As the extractant, 2-ethylhexanol alone or a mixture of 2-ethylhexanol with an extraction solvent such as kerosene (kerosene), heptane, nonane, decane, chloroform, carbon tetrachloride, xylene, benzene, etc. For example, in the case of kerosene, it is preferable to use a mixture obtained by mixing and diluting 2-ethylhexanol: kerosine = 1: 0.1 to 2 (volume ratio).
【００３３】図１においては、本発明の抽出方法をホウ
素の抽出、逆抽出及び晶析に適用した例を示したが、本
発明はホウ素に限らず、ｐＨによる溶解度差を利用して
逆抽出及び晶析を行う抽出方法であれば、いずれも有効
に適用可能であり、このような被抽出物質としては、ホ
ウ素の他、金属、非金属等が挙げられる。FIG. 1 shows an example in which the extraction method of the present invention is applied to the extraction, back extraction and crystallization of boron. However, the present invention is not limited to boron, and the back extraction is carried out by utilizing a solubility difference depending on pH. Any of the extraction methods for performing crystallization and crystallization can be effectively applied. Examples of such a substance to be extracted include metals, nonmetals, and the like in addition to boron.
【００３４】[0034]
【実施例】以下に実験例、実施例及び比較例を挙げて本
発明をより具体的に説明する。The present invention will be described below more specifically with reference to experimental examples, examples and comparative examples.
【００３５】実験例１ 図１に示す逆抽出及び晶析プロセスにおいて、逆抽出後
の逆抽出剤のｐＨを一定にするためには、変動するホウ
素濃度に対して逆抽出前の逆抽出剤に適正量のアルカリ
を添加する必要がある。EXPERIMENTAL EXAMPLE 1 In the back extraction and crystallization process shown in FIG. 1, in order to keep the pH of the back extraction agent after back extraction constant, the back extraction agent before back extraction should be used for a varying boron concentration. It is necessary to add an appropriate amount of alkali.
【００３６】そこで任意の逆抽出前のｐＨの逆抽出剤
（いずれもホウ素濃度２２０００ｍｇ／ＬのＮａＯＨ水
溶液）で逆抽出し、任意の逆抽出後ｐＨになった際のホ
ウ素逆抽出量を実験で求め、図２に示す結果を得た。こ
の結果は、任意の逆抽出ｐＨ（逆抽出前の逆抽出剤のｐ
Ｈ）で運転を行っているとき、逆抽出後の逆抽出剤ｐＨ
を測定すれば、その時の逆抽出剤中のホウ素濃度が分か
ることを示している。そして、ホウ素濃度が分かれば、
この濃度に対して逆抽出後ｐＨが設計値になるようにア
ルカリを添加すれば良いことになる。Therefore, back-extraction was carried out with a back-extracting agent having a pH before any back-extraction (both in a NaOH aqueous solution having a boron concentration of 22000 mg / L), and the amount of back-boron extraction when the pH reached after any back-extraction was determined by experiments. As a result, the results shown in FIG. 2 were obtained. This result can be obtained at any back extraction pH (p of the back extraction agent before back extraction).
H) When the operation is performed, the pH of the back extraction agent after back extraction
Indicates that the concentration of boron in the back extractant at that time can be determined. And if you know the boron concentration,
It suffices to add an alkali so that the pH becomes the designed value after the back extraction with respect to this concentration.
【００３７】例えば、図２から逆抽出前の逆抽出剤のｐ
Ｈ初期設定値を１３．１、逆抽出後の逆抽出剤のｐＨ設
定値を１２．２とした場合、ホウ素逆抽出量は約１２８
０ｍｇ／Ｌである。なお、この逆抽出量は逆抽出剤中の
ホウ素増加量であり、抽出剤中のホウ素濃度ではない。
従って、例えば、抽出剤と逆抽出剤の容量比を４で逆抽
出した場合、抽出剤中のホウ素濃度の低減量は３２０ｍ
ｇ／Ｌであったことになる。For example, from FIG.
When the H initial set value is 13.1, and the pH set value of the back extraction agent after back extraction is 12.2, the amount of boron back extraction is about 128.
0 mg / L. The amount of back extraction is an increase in boron in the back extractant, not the concentration of boron in the extractant.
Therefore, for example, when the volume ratio between the extractant and the back-extractant is back-extracted at 4, the reduction amount of the boron concentration in the extractant is 320 m
g / L.
【００３８】ここで、仮りに抽出剤中のホウ素濃度が低
くなり逆抽出量が８６５ｍｇ／Ｌとなった場合、逆抽出
後ｐＨは１２．６になると推定される。この逆抽出後の
逆抽出剤のｐＨ低下を防止して、逆抽出後の逆抽出剤の
ｐＨを１２．２に維持するためには、ホウ素８６５ｍｇ
／Ｌを逆抽出することでｐＨ１２．２となるような逆抽
出前の逆抽出剤ｐＨを設定すれば良い。この値は、図２
の横軸（Ｘ軸）のｐＨ１３．１から、ｐＨ１２．６の曲
線に垂線を引き（即ち、逆抽出量８６５ｍｇ／Ｌ）、こ
の交点ＡからｐＨ１２．２の曲線に向けて水平な線を引
き、この交点Ｂから横軸に垂直に下ろした点Ｃ、即ち、
ｐＨ１２．９２である。この値が逆抽出前の逆抽出剤の
ｐＨの設定値となる。Here, if the boron concentration in the extractant decreases and the amount of back-extraction becomes 865 mg / L, the pH after back-extraction is estimated to be 12.6. In order to prevent the pH of the back extraction agent after back extraction from lowering and maintain the back extraction agent pH at 12.2 after the back extraction, 865 mg of boron is used.
What is necessary is just to set the back extraction agent pH before back extraction so that it may become pH 12.2 by back extracting / L. This value is shown in FIG.
From pH 13.1 on the horizontal axis (X-axis), a perpendicular line is drawn to the curve of pH 12.6 (that is, 865 mg / L of back-extraction amount), and a horizontal line is drawn from the intersection A toward the curve of pH 12.2. , A point C vertically lowered from the intersection B to the horizontal axis, that is,
pH is 12.92. This value is the set value of the pH of the back extraction agent before back extraction.
【００３９】このように逆抽出後の逆抽出剤のｐＨを測
定し、その値から適正な逆抽出前の逆抽出剤のｐＨを設
定してｐＨ調整することで逆抽出後の逆抽出剤のｐＨを
逆抽出及び晶析に適当な設定値に維持することができ
る。As described above, the pH of the back-extracting agent after back-extraction is measured, and the pH of the back-extracting agent after back-extraction is adjusted by setting the appropriate pH of the back-extracting agent before back-extraction based on the measured value. The pH can be maintained at a suitable setting for back extraction and crystallization.
【００４０】なお、この関係は逆抽出前の逆抽出剤中に
含まれるホウ素濃度により変わるので、設定条件に合わ
せて求める必要がある。Since this relationship varies depending on the concentration of boron contained in the back extraction agent before back extraction, it is necessary to find the relationship in accordance with the set conditions.
【００４１】実施例１ 図１に示す逆抽出、晶析装置を用いてホウ素を抽出した
抽出剤からのホウ素の逆抽出及び晶析を行った。Example 1 Back-extraction and crystallization of boron from an extracting agent from which boron was extracted were performed using the back-extraction and crystallization apparatus shown in FIG.
【００４２】逆抽出塔としては、ミキサー部容量９Ｌ、
セトラー部容量４８Ｌの抽出塔を１塔用い、ホウ素を抽
出した抽出剤（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もの）を４０Ｌ／ｈｒで連続
的に供給すると共に、逆抽出剤としてＮａＯＨ水溶液
（ホウ素濃度２２０００ｍｇ／Ｌ）を１５Ｌ／ｈｒで供
給した。なお逆抽出塔のミキサー部の温度は２５℃、晶
析槽の温度は１０℃であった。As the back extraction column, the mixer section capacity was 9 L,
Using one extraction column having a settler volume of 48 L, an extractant (a mixture of 2-ethylhexanol and kerosene mixed at a volume ratio of 1: 1) from which boron was extracted was continuously supplied at a rate of 40 L / hr, An aqueous NaOH solution (boron concentration: 22000 mg / L) was supplied at 15 L / hr as a back extraction agent. In addition, the temperature of the mixer part of the back extraction tower was 25 degreeC, and the temperature of the crystallization tank was 10 degreeC.
【００４３】逆抽出後の逆抽出剤の設定ｐＨは１２．３
とした。The set pH of the back extraction agent after back extraction is 12.3.
And
【００４４】〈Ｒｕｎ １〉逆抽出塔にホウ素濃度３７
０ｍｇ／Ｌの抽出剤を供給し、逆抽出剤のｐＨ（逆抽出
前）１３．１で運転を開始したところ、逆抽出後の逆抽
出剤のｐＨが安定した時点で、逆抽出後の逆抽出剤のｐ
Ｈは１２．５であったため、ｐＨ調整槽２へのＮａＯＨ
添加量を変えて、逆抽出剤のｐＨ（逆抽出前）を１３．
０に変更した。その結果、逆抽出後の逆抽出剤のｐＨは
１２．２４に下がった。<Run 1> A boron concentration of 37 was added to the back extraction column.
0 mg / L of the extractant was supplied, and the operation was started at a pH of 13.1 (before back-extraction) of the back-extraction agent. Extractant p
H was 12.5, so NaOH
12. The pH of the back-extraction agent (before back-extraction) is changed by changing the amount of addition.
Changed to 0. As a result, the pH of the back extraction agent after back extraction dropped to 12.24.
【００４５】〈Ｒｕｎ ２〉Ｒｕｎ１に続き、抽出剤を
ホウ素濃度４７０ｍｇ／Ｌの抽出剤に変更して逆抽出を
行ったところ、逆抽出後のｐＨが１１．９５となったの
で、ｐＨ調整槽２へのＮａＯＨ添加量を変えて、逆抽出
前の逆抽出剤のｐＨを１３．１とした。その結果、逆抽
出後の逆抽出剤のｐＨは１２．２６に上がった。<Run 2> Following Run 1, when the extractant was changed to an extractant having a boron concentration of 470 mg / L and back-extraction was performed, the pH after the back-extraction became 11.95. By changing the amount of NaOH added to 2, the pH of the back extraction agent before back extraction was set to 13.1. As a result, the pH of the back extraction agent after back extraction rose to 12.26.
【００４６】〈Ｒｕｎ ３〉Ｒｕｎ２に続き、抽出剤を
ホウ素濃度５６０ｍｇ／Ｌの抽出剤に変更して逆抽出を
行ったところ、逆抽出後の逆抽出剤のｐＨは１２．０と
なったので、ｐＨ調整槽２へのＮａＯＨ添加量を変え
て、逆抽出前の逆抽出剤のｐＨを１３．２とした。その
結果、逆抽出後の逆抽出剤のｐＨは１２．２８に上がっ
た。<Run 3> Following Run 2, when the extractant was changed to an extractant having a boron concentration of 560 mg / L and back-extraction was performed, the pH of the back-extractant after back-extraction was 12.0. By changing the amount of NaOH added to the pH adjusting tank 2, the pH of the back extraction agent before back extraction was set to 13.2. As a result, the pH of the back extraction agent after back extraction rose to 12.28.
【００４７】このように、逆抽出後の逆抽出剤のｐＨが
約１２．３で一定となるように、逆抽出前の逆抽出剤に
添加するＮａＯＨ量を制御してｐＨ調整を行ったとこ
ろ、逆抽出剤中には、抽出剤中のホウ素が逆抽出され、
この逆抽出されたホウ素は、そのほぼ全量が晶析槽にて
析出し、結晶として回収された。Thus, the pH was adjusted by controlling the amount of NaOH added to the back extraction agent before back extraction so that the pH of the back extraction agent after back extraction was constant at about 12.3. In the back extraction agent, boron in the extraction agent is back extracted,
Almost all of the back-extracted boron was precipitated in the crystallization tank and recovered as crystals.
【００４８】比較例１ 実施例１のＲｕｎ１終了後、Ｒｕｎ２、Ｒｕｎ３と他の
条件は同じで逆抽出前の逆抽出剤のｐＨ制御を行わずに
ｐＨ１３．０のままで運転を行った。その結果、逆抽出
不良により、逆抽出塔及び逆抽出後の抽出剤の配管等に
結晶が析出し、連続運転が困難となった。COMPARATIVE EXAMPLE 1 After the completion of Run 1 in Example 1, Run 2 and Run 3 were performed under the same conditions except that the pH of the back extraction agent before back extraction was not controlled and the pH was kept at 13.0. As a result, due to poor back extraction, crystals were precipitated in the back extraction tower and the piping of the extraction agent after back extraction, and continuous operation became difficult.
【００４９】[0049]
【発明の効果】以上詳述した通り、本発明の抽出方法に
よれば、抽出部において被処理水を抽出剤と接触させて
該被処理水中のホウ素等の目的物質を該抽出剤中に抽出
した後、逆抽出部において該目的物質を抽出した抽出剤
を逆抽出剤と接触させて該目的物質を該逆抽出剤中に逆
抽出し、さらに該逆抽出剤中の該目的物質を晶析回収す
る抽出方法において、逆抽出前後の逆抽出剤のｐＨを適
正に抑制することにより、不可変動、即ち被処理水中の
目的物質濃度の変動に十分応じて抽出、逆抽出及び晶析
回収までの一連の処理を安定かつ効率的に行うことが可
能とされる。As described in detail above, according to the extraction method of the present invention, the water to be treated is brought into contact with the extractant in the extraction section to extract the target substance such as boron in the water to be treated into the extractant. After that, in the back-extraction section, the extractant from which the target substance is extracted is brought into contact with the back-extractant to back-extract the target substance into the back-extractant, and the target substance in the back-extractant is crystallized. In the extraction method to be recovered, by appropriately controlling the pH of the back-extracting agent before and after back-extraction, the extraction, back-extraction and crystallization recovery can be performed in accordance with the unchangeable, that is, the fluctuation of the target substance concentration in the water to be treated. A series of processes can be performed stably and efficiently.
【図１】本発明の抽出方法の実施の形態を示す系統図で
ある。FIG. 1 is a system diagram showing an embodiment of an extraction method according to the present invention.
【図２】逆抽出剤のｐＨとホウ素の逆抽出量との関係を
示すグラフである。FIG. 2 is a graph showing the relationship between the pH of a back extraction agent and the amount of back extraction of boron.
１ 逆抽出剤槽 ２ ｐＨ調整槽 ２Ａ，４Ａ ｐＨ計 ３ 逆抽出塔 ４ 晶析槽 Ｐ1，Ｐ2，Ｐ3 ポンプ1 reverse extractant tank 2 pH adjustment tank 2A, 4A pH meter 3 stripping column 4 crystalliser P 1, P 2, P 3 pump
───────────────────────────────────────────────────── フロントページの続き (72)発明者 野口 嘉一 東京都中央区銀座六丁目15番１号 電源開 発株式会社内 (72)発明者 武藤 憲一 神奈川県横浜市磯子区新磯子町37の２ 電 源開発株式会社磯子火力発電所内 (72)発明者 砥山 浩司 大阪府大阪市北区中之島３丁目３番22号 関西電力株式会社内 (72)発明者 山下 直之 大阪府大阪市北区中之島３丁目３番22号 関西電力株式会社内 (72)発明者 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 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 Ｆターム(参考） 4D037 AA11 AB10 BA14 BB01 BB02 BB09 CA14 4D056 AB07 AB10 AC02 AC06 AC22 AC25 CA11 CA17 CA25 CA33 CA34 DA10 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kaichi Noguchi 6-15-1, Ginza, Chuo-ku, Tokyo Inside Power Development Co., Ltd. (72) Inventor Kenichi Muto 37 Shinisogo-cho, Isogo-ku, Yokohama-shi, Kanagawa 2 Power Development Co., Ltd. Isogo Thermal Power Station (72) Koji Toyama 3-3-22 Nakanoshima, Kita-ku, Osaka-shi, Osaka Prefecture Kansai Electric Power Co., Inc. (72) Naoyuki Yamashita 3 Nakanoshima, Kita-ku, Osaka-shi, Osaka 3-22, Kansai Electric Power Co., Inc. (72) Inventor Hiroyuki Asada 3-4-7, Nishi-Shinjuku, Shinjuku-ku, Tokyo Kurita Industrial Co., Ltd. No.4-7 Kurita Kogyo Co., Ltd. F term (reference) 4D037 AA11 AB10 BA14 BB01 BB02 BB09 CA14 4D056 AB07 AB10 AC02 AC06 AC22 AC25 CA11 CA17 CA25 CA33 CA34 DA10
Claims (2)
させて該被処理水中の目的物質を該抽出剤中に抽出した
後、逆抽出部において該目的物質を抽出した抽出剤を逆
抽出剤と接触させて該目的物質を該逆抽出剤中に逆抽出
し、更に該逆抽出剤中の該目的物質を晶析させて回収す
る抽出方法において、 逆抽出後の逆抽出剤のｐＨ値に基いて、逆抽出前の逆抽
出剤のｐＨ値を調整することを特徴とする抽出方法。1. An extractor contacts the water to be treated with an extractant to extract a target substance in the water to be extracted into the extractant, and then back-extracts the extractant from which the target substance is extracted in a back extractor. A back-extraction agent, the target substance is back-extracted into the back-extracting agent, and the target substance in the back-extracting agent is crystallized and recovered. And adjusting the pH value of the back-extraction agent before back-extraction based on the method.
抽出剤のｐＨ値は、ｐＨ調整剤の添加量により制御する
ことを特徴とする抽出方法。2. The method according to claim 1, wherein the pH value of the back extraction agent before back extraction is controlled by the amount of the pH adjuster added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36108898A JP4200567B2 (en) | 1998-12-18 | 1998-12-18 | Extraction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36108898A JP4200567B2 (en) | 1998-12-18 | 1998-12-18 | Extraction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000176438A true JP2000176438A (en) | 2000-06-27 |
| JP4200567B2 JP4200567B2 (en) | 2008-12-24 |
Family
ID=18472153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36108898A Expired - Fee Related JP4200567B2 (en) | 1998-12-18 | 1998-12-18 | Extraction method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4200567B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106474766A (en) * | 2016-11-30 | 2017-03-08 | 广东技术师范学院 | A kind of sucralose low energy consumption extraction equipment |
| US20220105446A1 (en) * | 2020-10-02 | 2022-04-07 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Extraction system |
-
1998
- 1998-12-18 JP JP36108898A patent/JP4200567B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106474766A (en) * | 2016-11-30 | 2017-03-08 | 广东技术师范学院 | A kind of sucralose low energy consumption extraction equipment |
| US20220105446A1 (en) * | 2020-10-02 | 2022-04-07 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Extraction system |
| JP2022059818A (en) * | 2020-10-02 | 2022-04-14 | 株式会社神戸製鋼所 | Extraction system |
| JP7394731B2 (en) | 2020-10-02 | 2023-12-08 | 株式会社神鋼環境ソリューション | extraction system |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4200567B2 (en) | 2008-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5876685A (en) | Separation and purification of fluoride from industrial wastes | |
| EP1797221A2 (en) | Synthesis of hydrogen peroxide | |
| US3554692A (en) | Recovery of copper and vanadium from a solution containing iron | |
| JP6972042B2 (en) | Recycling method of liquid nuclear waste by controlling boron concentration | |
| JP2000176438A (en) | Extraction method | |
| JPH11309464A (en) | Crystallization dephosphorization method and its device | |
| JP4385421B2 (en) | Boron extraction method | |
| JP3336858B2 (en) | Method for treating boron-containing water | |
| US5277817A (en) | Apparatus and methods for treating electroless plating baths | |
| JP2005509163A (en) | Method and apparatus for the treatment of radioactive waste | |
| KR19990028257A (en) | Method for Purifying Liquid Medium by Extraction | |
| JP3918294B2 (en) | Method and apparatus for treating fluorine-containing wastewater | |
| US5524780A (en) | Control of regeneration of ammoniacal copper etchant | |
| JP3438534B2 (en) | Treatment method of boron-containing water | |
| JPH0315512B2 (en) | ||
| CN111420964A (en) | Method and device for processing miscellaneous salt | |
| EP1399387A1 (en) | Process for removing sodium sulfate from nickel hydroxide effluent streams | |
| RU2777641C1 (en) | Method for regenerating spent sulphuric acid after alkylation | |
| JP3493954B2 (en) | Extraction method | |
| JP2002292202A (en) | Crystallization reaction apparatus provided with means for recovering crystallization-reactive component | |
| Hou et al. | Bipolar membrane crystallization enables near zero-waste production of high-purity oxalic acid crystals | |
| JPH0150476B2 (en) | ||
| RU2213064C1 (en) | Method of recovering ethylenediaminetetraacetic acid from spent washing solution in power station steam generators | |
| CN118047493A (en) | Thiazole zinc wastewater treatment process | |
| JPH06317697A (en) | Circulating disposal method for radioactive waste liquid containing sodium nitrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051124 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080319 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080325 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080523 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080624 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080820 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080916 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080929 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111017 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111017 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121017 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121017 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131017 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |