JP2002079115A - METHOD AND APPARATUS FOR RECOVERING Cr(VI) FROM ANION EXCHANGE RESIN TOWER - Google Patents
METHOD AND APPARATUS FOR RECOVERING Cr(VI) FROM ANION EXCHANGE RESIN TOWERInfo
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- JP2002079115A JP2002079115A JP2000268913A JP2000268913A JP2002079115A JP 2002079115 A JP2002079115 A JP 2002079115A JP 2000268913 A JP2000268913 A JP 2000268913A JP 2000268913 A JP2000268913 A JP 2000268913A JP 2002079115 A JP2002079115 A JP 2002079115A
- Authority
- JP
- Japan
- Prior art keywords
- liquid
- exchange resin
- recovering
- ion exchange
- anion exchange
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/203—Equilibration or regeneration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
- B01D15/361—Ion-exchange
- B01D15/363—Anion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、Ｃｒ（VI）、ＳＯ
4 2- 、Ｃｌ-イオン等を吸着して吸着飽和したイオン交
換樹脂から、Ｃｒ（VI）を高濃度で効率よく回収する方
法及び回収装置に関する。[0001] The present invention relates to Cr (VI), SO
4 2-, Cl - ion exchange resin adsorbed saturated by adsorbing ions, to a method and recovery apparatus for efficiently recovering Cr and (VI) at high concentrations.
【０００２】[0002]
【従来の技術】クロメートあるいはクロムメッキ工場に
おいて発生する６価クロム含有水洗水の可搬式イオン交
換塔による処理法として、陰イオン交換樹脂を充填した
イオン交換塔にて有害なＣｒ（VI）のみを吸着除去する
方法、あるいは陽イオン交換樹脂と陰イオン交換樹脂と
でカチオン、アニオン（Ｃｒ（VI）以外のアニオンも含
む）を全て吸着除去し、処理水は純水として系内で再利
用する方法がある。2. Description of the Related Art As a treatment method of hexavalent chromium-containing washing water generated in a chromate or chromium plating plant by a portable ion exchange tower, only harmful Cr (VI) is used in an ion exchange tower filled with an anion exchange resin. A method of adsorbing and removing, or a method of adsorbing and removing all cations and anions (including anions other than Cr (VI)) between the cation exchange resin and the anion exchange resin, and reusing the treated water as pure water in the system There is.
【０００３】いずれの方法も、需要家で吸着飽和したイ
オン交換塔は、専用の車で集中再生場まで運び再生作業
を行なう必要があった。集中再生場における再生方法
は、通常、需要家で吸着飽和したイオン交換樹脂を充填
したイオン交換塔を再生スタンドに並列に並べ、向流多
段再生するという方法が採用されている。なお、需要家
には代わりの再生済みのイオン交換塔が設置され、連続
使用されることになる。[0003] In any of the methods, the ion-exchange tower that has been adsorbed and saturated by the customer must be transported to a centralized regeneration site by a dedicated car and regenerated. As a regeneration method in a centralized regeneration plant, a method of arranging an ion exchange tower filled with an ion exchange resin saturated and adsorbed by a customer in parallel on a regeneration stand and performing countercurrent multistage regeneration is usually employed. In addition, the customer will be provided with an alternative regenerated ion exchange tower, which will be used continuously.
【０００４】回収したＣｒ（VI）液は、三酸化クロム又
はクロム化合物の製造原料として有効利用するのが環境
保全の意味からも最も望ましい方法である。しかし、従
来の向流多段再生法の場合、上述したように需要家で使
用済みの吸着飽和した陰イオン交換樹脂には、Ｃｒ（V
I）以外にＳＯ4 2- 、Ｃｌ- イオン等も吸着している。
このため、これらのイオンも回収Ｃｒ（VI）液中に混入
してくるため、更に精製処理を施す必要が生じるという
問題があった。It is the most desirable method to effectively use the recovered Cr (VI) liquid as a raw material for producing chromium trioxide or a chromium compound from the viewpoint of environmental protection. However, in the case of the conventional countercurrent multistage regeneration method, as described above, the adsorption-saturated anion-exchange resin used by the customer contains Cr (V
In addition to I), SO 4 2− and Cl − ions are also adsorbed.
For this reason, these ions are also mixed into the recovered Cr (VI) liquid, and there is a problem that it is necessary to perform a further purification treatment.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、かかる事情
に鑑みてなされたものであり、その課題とするところは
回収したＣｒ（VI）液中の不純物を容易に低減でき、ク
ロム塩類の製造原料として使用可能となる方法及び装置
を提供する。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to make it possible to easily reduce impurities in a recovered Cr (VI) solution and to produce chromium salts. Provided are a method and an apparatus which can be used as a raw material.
【０００６】[0006]
【課題を解決するための手段】この課題を解決するため
に、本発明は、Ｃｒ（VI）、ＳＯ4 2- 、Ｃｌ- イオン等
の吸着飽和した陰イオン交換樹脂塔から、Ｃｒ（VI）の
みを高濃度で回収する方法において、Ｃｒ（VI）高濃度
液を通液して、ＳＯ4 2- 、Ｃｌ-イオン等を押し出す工
程と、向流多段再生法を行なう工程とを有することを特
徴とするＣｒ（VI）の高濃度回収方法である。In order to solve this problem, the present invention provides a method for producing a Cr (VI), SO 4 2- , Cl - ion or the like from an anion-exchange resin tower saturated with adsorption. The method of recovering only high-concentration only has a step of extruding SO 4 2− , Cl − ions and the like by passing a Cr (VI) high concentration liquid, and a step of performing a countercurrent multistage regeneration method. This is a high concentration recovery method for Cr (VI), which is a feature.
【０００７】また、本発明は、通液するＣｒ（VI）濃厚
液は、向流多段再生法で得た液を再利用することを特徴
とするＣｒ（VI）の高濃度回収方法である。更に本発明
は、再生はイオン交換塔を複数塔並べて同時再生するこ
とを特徴とするＣｒ（VI）の高濃度回収方法である。Further, the present invention is a method for recovering a high concentration of Cr (VI), characterized in that a liquid obtained by a countercurrent multistage regeneration method is reused as a concentrated Cr (VI) liquid to be passed. Further, the present invention is a method for recovering Cr (VI) at a high concentration, wherein regeneration is performed by arranging a plurality of ion exchange towers simultaneously.
【０００８】また、本発明は、Ｃｒ（VI）、ＳＯ4 2- 、
Ｃｌ- イオン等の吸着飽和した陰イオン交換樹脂塔を充
填したイオン交換塔と、このイオン交換塔内のイオン交
換樹脂を再生するための再生液を充填した向流多段再生
法を行うための複数の再生液タンクと、第１の再生液タ
ンクからイオン交換塔を通液して得られた液を入れるＣ
ｒ（VI）濃厚液タンク及び回収液タンクとを具備したＣ
ｒ（VI）の高濃度回収装置である。Further, the present invention provides a method for producing Cr (VI), SO 4 2- ,
An ion exchange tower filled with an anion exchange resin tower saturated with adsorption of Cl 2 -ions and the like, and a plurality of countercurrent multistage regeneration methods filled with a regenerating liquid for regenerating the ion exchange resin in the ion exchange tower. And the liquid obtained by passing the liquid from the first regenerating liquid tank through the ion exchange tower.
r (VI) C equipped with a concentrated liquid tank and a recovery liquid tank
It is a high concentration recovery device for r (VI).
【０００９】[0009]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明方法では、向流多段再生を行なう前に、需要家で
吸着飽和した陰イオン交換樹脂塔に不純物の少ないＣｒ
（VI）濃厚液を通液し、吸着しているＳＯ4 2-、Ｃｌ-
イオン等の押し出しを行なった後に、引き続き、向流多
段再生を行なう。そして、使用するCr（VI）濃厚液は、
一度、向流多段再生を行って得られたＣｒ（VI）液を再
使用することにより、新たな無水クロム酸等の購入が不
要になる。また、向流多段再生はイオン交換塔を複数塔
並べて同時再生を行うことにより、濃縮効率の向上、作
業時間の短縮につながる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the method of the present invention, before performing countercurrent multi-stage regeneration, the anion-exchange resin tower, which has been adsorbed and saturated by the customer, has a low impurity Cr content.
(VI) SO 4 2− , Cl − adsorbed through the concentrated solution
After extruding ions or the like, countercurrent multistage regeneration is subsequently performed. And the Cr (VI) concentrate used is
By reusing the Cr (VI) solution obtained by performing the countercurrent multistage regeneration once, it becomes unnecessary to purchase new chromic anhydride or the like. In the countercurrent multi-stage regeneration, by performing simultaneous regeneration by arranging a plurality of ion exchange towers, it is possible to improve the concentration efficiency and shorten the operation time.
【００１０】通液するＣｒ（VI）濃厚液は、全ての使用
済み陰イオン交換樹脂塔に同量通液する必要はなく、個
々に通液量も異なるので個々に監視する必要がある。そ
の理由は、需要家にて通液する液種、通液条件等によっ
て、陰イオン交換樹脂へのＣｒ（VI）吸着度合は様々で
あるからである。Ｃｒ（VI）イオンは有色イオンである
ため、吸着すると、イオン交換樹脂の色が黄色あるいは
オレンジ色に呈してくるので、Ｃｒ（VI）イオンが多く
吸着して飽和したイオン交換塔の場合、通液するＣｒ
（VI）量は少なくてすみ、逆にＣｒ（VI）イオンが少な
く吸着しているような場合、通液量は多く必要となる。
従って、樹脂の着色状況を容易に目視で確認できるよう
にイオン交換塔の側面には覗窓が上方及び下方に最低２
箇所設けられていることが望ましい。なお、必要通液量
を自動的に検知し、検知信号に基づいて通液の停止を行
うことも可能である。It is not necessary to pass the same amount of the passed Cr (VI) concentrate through all the used anion exchange resin towers, and it is necessary to monitor them individually since the flow rates differ from one another. The reason for this is that the degree of Cr (VI) adsorption to the anion exchange resin varies depending on the type of liquid to be passed by the customer, the conditions for passing through, and the like. Since the Cr (VI) ion is a colored ion, the color of the ion-exchange resin becomes yellow or orange when adsorbed. Therefore, in the case of an ion-exchange column saturated with a large amount of Cr (VI) ion adsorbed, Liquid Cr
In the case where the amount of (VI) is small and the amount of Cr (VI) ion adsorbed is small, a large amount of liquid is required.
Therefore, in order to easily check the coloration state of the resin visually, there are at least two viewing windows on the side of the ion exchange tower at the top and bottom.
It is desirable to be provided at a location. In addition, it is also possible to automatically detect the required flow amount and stop the flow based on the detection signal.
【００１１】Ｃｒ（ＶＩ）濃度は濃いほど、ＳＯ4 2- 、
Ｃｌ- イオン等の不純物陰イオンを押出すのに効果があ
る。Ｃｒ（ＶＩ）濃度としては、できれば１０ｇ／Ｌ以
上で濃いほどよいが、あまり濃すぎるとイオン交換樹脂
は劣化する。又、イオン交換樹脂は有機物であるため、
安全性の点から上限は１００ｇ／Ｌ以下が望ましい。As the Cr (VI) concentration becomes higher, SO 4 2− ,
It is effective in extruding impurity anions such as Cl - ions. The concentration of Cr (VI) is preferably as high as 10 g / L or more if possible, but if it is too high, the ion-exchange resin deteriorates. Also, since ion exchange resins are organic substances,
From the viewpoint of safety, the upper limit is desirably 100 g / L or less.
【００１２】また、Ｃｒ（ＶＩ）を吸着させるために通
液するＣｒ（ＶＩ）濃厚液のｐＨは酸性側に調整してお
く必要がある。しかし、得られた回収液をクロム酸類の
原料として使用する場合、回収液中のＣｌ−，ＳＯ４
２−濃度を極力少なくするため、６．５〜７．０位が望
ましい。ｐＨ調整用の酸としては、硫酸、又は塩酸が望
ましい。その他、通液するＣｒ（ＶＩ）濃厚液のＣｒ
（ＶＩ）濃度が低い場合、濃縮器で濃縮して使用すると
いう方法も可能である。Further, it is necessary to adjust the pH of the concentrated Cr (VI) solution passed therethrough to adsorb Cr (VI) to the acidic side. However, when the obtained recovered liquid is used as a raw material of chromic acids, Cl − and SO 4 in the recovered liquid are used.
2- In order to reduce the concentration as much as possible, it is desirable to be about 6.5 to 7.0. Sulfuric acid or hydrochloric acid is desirable as the acid for pH adjustment. In addition, Cr (VI) concentrated liquid
(VI) When the concentration is low, a method of concentrating and using a concentrator is also possible.
【００１３】なお、通液するＣｒ（VI） 濃厚液に懸濁
物が含まれている場合、あらかじめフィルタープレスな
どのろ過機にて除去しておく必要がある。[0013] If a suspension is contained in the concentrated Cr (VI) solution to be passed through, it must be removed in advance by a filter such as a filter press.
【００１４】[0014]
【実施例】本発明のＣｒ（VI）の高濃度回収法について
図１に示す実施例に基づき説明する。なお、図１は向流
３段法での場合で、陰イオン交換樹脂塔には弱塩基性陰
イオン交換樹脂が充填されている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The method for recovering a high concentration of Cr (VI) according to the present invention will be described with reference to the embodiment shown in FIG. FIG. 1 shows the case of a three-stage countercurrent method, in which the anion exchange resin column is filled with a weakly basic anion exchange resin.
【００１５】（押出し工程）まず、需要家で吸着飽和し
た陰イオン交換樹脂塔５を集中再生場に持ち込み、樹脂
に付着した夾雑物を除去するため水洗浄を行なった後
（ただし、図１には記載されていない）、再生スタンド
１７に配置接続する。再生スタンド１７には他の需要家
で使用済みのイオン交換塔６〜８も同様に所定の位置に
配置接続する。(Extrusion step) First, an anion-exchange resin tower 5 that has been adsorbed and saturated by a customer is brought to a centralized regeneration plant, and washed with water to remove impurities adhering to the resin (see FIG. 1). Are not described), and are arranged and connected to the reproduction stand 17. Ion exchange towers 6 to 8 used by other consumers are similarly arranged and connected to the regeneration stand 17 at predetermined positions.
【００１６】Ｃｒ（VI）濃厚液タンク４には、硫酸溶液
１５でｐＨ６．５に調整したＣｒ（VI）濃厚液が入って
おり、この液をバルブ４ａ，ポンプ１４を介してバルブ
５ａ，５ｂ，６ａ，６ｂ，７ａ，７ｂ，８ａ，８ｂを経
由して所定位置に設置した４塔の陰イオン交換樹脂塔５
〜８に同時に通液し、処理水はバルブ５ｃ，５ｄ，６
ｃ，６ｄ，７ｃ，７ｄ，８ｃ，８ｄを通り、さらにバル
ブ１６ａを介して排水１６に流す（以後、クロム再吸着
工程と称する。また、バルブの開閉については、特に指
定しない限り、イオン交換塔上部及び下部接続用バルブ
５ａ〜５ｄ、７ａ〜７ｄ、８ａ〜８ｄは、常時開いてい
る状態とし、それ以外は記述した場合のみ開いている状
態を示すものとする。） 通液終了の目安は、それぞれのイオン交換塔の処理水に
Ｃｒ（VI）濃厚液同様の色が目視で認められた時点で個
々のイオン交換塔入口のバルブを閉め、全ての通液が終
了した時点とする。以上でクロム再吸着工程は終了とな
り、次の向流多段再生工程へと移行する。The Cr (VI) concentrated liquid tank 4 contains a Cr (VI) concentrated liquid adjusted to pH 6.5 with a sulfuric acid solution 15, and this liquid is supplied to the valves 5a and 5b via a valve 4a and a pump 14. , 6a, 6b, 7a, 7b, 8a, 8b, four anion exchange resin towers 5 installed at predetermined positions
Through 8 at the same time, and the treated water flows through valves 5c, 5d, 6
c, 6d, 7c, 7d, 8c, 8d, and then to drain 16 via valve 16a (hereinafter referred to as a chromium re-adsorption step. The opening and closing of the valve is performed unless otherwise specified. The upper and lower connection valves 5a to 5d, 7a to 7d, and 8a to 8d are always open, and the other states are open only when described. At the time when the same color as the Cr (VI) concentrated liquid is visually observed in the treated water of each ion exchange tower, the valves at the inlets of the individual ion exchange towers are closed, and the time when all the liquid passing is completed. Thus, the chromium re-adsorption process is completed, and the process proceeds to the next countercurrent multistage regeneration process.
【００１７】ここで、クロム再吸着工程を行うために設
置する陰イオン交換塔にＣｒ（VI）液が多量に吸着して
いれば、Ｃｒ（VI）濃厚タンク４からの通液量が少なく
てすみ、Ｃｒ（VI）濃厚タンク４の液量はあまり減るこ
とがない。逆に、設置した陰イオン交換塔の樹脂にＣｒ
（VI）がほとんど吸着していなければ、クロム再吸着工
程でＣｒ（VI）濃厚タンク４から多量の液を通液する必
要がある。Here, if a large amount of the Cr (VI) liquid is adsorbed on the anion exchange column installed for performing the chromium re-adsorption step, the amount of liquid passed from the Cr (VI) concentrated tank 4 is small. In this case, the amount of liquid in the Cr (VI) rich tank 4 does not decrease so much. Conversely, Cr in the resin of the installed anion exchange tower
If almost no (VI) is adsorbed, it is necessary to pass a large amount of liquid from the Cr (VI) concentrated tank 4 in the chromium re-adsorption step.
【００１８】（向流多段再生工程）第1の再生液タンク
１の液の一定量をバルブ１ａ，ポンプ１３、バルブ１３
ａを介してバルブ５ａ，５ｂ，６ａ，６ｂ，７ａ，７
ｂ，８ａ，８ｂを経由して所定位置に設置した４塔の陰
イオン交換樹脂塔５〜８に同時通液した後、処理水はバ
ルブ５ｃ，５ｄ，６ｃ，６ｄ，７ｃ，７ｄ，８ｃ，８ｄ
を通り更にバルブ４ｂを通してＣｒ（VI）濃厚液タンク
４に入れる。この場合、Ｃｒ（VI）濃厚液タンク４に
は、クロム再吸着工程で減った液量だけ入り、補充され
るので、クロム再吸着工程を行うために設置する陰イオ
ン交換塔にＣｒ（VI）液が多量に吸着している場合と、
少量しか吸着していない場合とで、第１の再生液タンク
１からの液補充量は異なることとなる。そして、第１の
再生液タンク１の残存液は、バルブ１ａ，ポンプ１３、
バルブ１３ａを介してバルブ５ａ，５ｂ，６ａ，６ｂ，
７ａ，７ｂ，８ａ，８ｂを経由して所定位置に設置した
４塔の陰イオン交換樹脂塔５〜８に同時通液した後、処
理水はバルブ５ｃ，５ｄ，６ｃ，６ｄ，７ｃ，７ｄ，８
ｃ，８ｄを通り更にバルブ１２ａを通して回収液タンク
１２に入れる（これが、クロム塩類の原料用として利用
されることとなる）。そして、第１の再生液タンク１は
実質的に空になる。(Counterflow Multistage Regeneration Step) A certain amount of the liquid in the first regenerating liquid tank 1 is supplied to the valve 1a, the pump 13,
a through the valves 5a, 5b, 6a, 6b, 7a, 7
After passing simultaneously through four anion exchange resin towers 5 to 8 installed at predetermined positions via b, 8a, 8b, the treated water is supplied to valves 5c, 5d, 6c, 6d, 7c, 7d, 8c, 8c, 8d
And then into the Cr (VI) concentrated liquid tank 4 through the valve 4b. In this case, the Cr (VI) concentrated liquid tank 4 is replenished with the amount of the liquid reduced in the chromium re-adsorption step, so that the Cr (VI) concentrated liquid tank 4 is added to the anion exchange tower installed for performing the chromium re-adsorption step. When a large amount of liquid is adsorbed,
The amount of liquid replenishment from the first regenerating liquid tank 1 is different between the case where only a small amount is adsorbed. The remaining liquid in the first regenerating liquid tank 1 is supplied to the valve 1a, the pump 13,
The valves 5a, 5b, 6a, 6b,
After passing simultaneously through four anion exchange resin towers 5 to 8 installed at predetermined positions via 7a, 7b, 8a and 8b, the treated water is supplied to valves 5c, 5d, 6c, 6d, 7c, 7d, 8
After passing through c and 8d, the liquid is put into the recovery liquid tank 12 through the valve 12a (this is used as a raw material for chromium salts). Then, the first regenerating liquid tank 1 becomes substantially empty.
【００１９】引き続き、第２の再生液タンク２の液は、
バルブ２ａ，ポンプ１３、バルブ１３ａを介してバルブ
５ａ，５ｂ，６ａ，６ｂ，７ａ，７ｂ，８ａ，８ｂを経
由して４塔の陰イオン交換樹脂塔５〜８に通液した後、
処理水はバルブ５ｃ，５ｄ，６ｃ，６ｄ，７ｃ，７ｄ，
８ｃ，８ｄを通り更にバルブ１ｂを介して空の第1の再
生液タンク１に入る。この時、第２の再生液タンク２は
実質的に空になる。Subsequently, the liquid in the second regenerating liquid tank 2
After passing through four anion exchange resin towers 5 to 8 via valves 5a, 5b, 6a, 6b, 7a, 7b, 8a, 8b via valve 2a, pump 13 and valve 13a,
The treated water is supplied to valves 5c, 5d, 6c, 6d, 7c, 7d,
After passing through 8c and 8d, it enters the empty first regenerating liquid tank 1 via the valve 1b. At this time, the second regenerating liquid tank 2 is substantially empty.
【００２０】同様に、第３の再生液タンク３の液は、バ
ルブ３ａ，ポンプ１３、バルブ１３ａを介してバルブ５
ａ，５ｂ，６ａ，６ｂ，７ａ，７ｂ，８ａ，８ｂを経由
して４塔の陰イオン交換樹脂塔５〜８に通液した後、処
理水はバルブ５ｃ，５ｄ，６ｃ，６ｄ，７ｃ，７ｄ，８
ｃ，８ｄを通り更にバルブ２ｂを介して空の第２の再生
液タンク２に入る。ここでも第３の再生液タンク３は実
質的に空になる。Similarly, the liquid in the third regenerating liquid tank 3 is supplied to the valve 5 via the valve 3a, the pump 13, and the valve 13a.
a, 5b, 6a, 6b, 7a, 7b, 8a, 8b, and after passing through the four anion exchange resin towers 5 to 8 through 8b, the treated water is supplied to the valves 5c, 5d, 6c, 6d, 7c, 7d, 8
The liquid enters the empty second regenerating liquid tank 2 through the valves c and 8d and further via the valve 2b. Here again, the third regenerating liquid tank 3 is substantially empty.
【００２１】そして、エアー１０のバルブ１０ａが開
き、バルブ５ａ，５ｂ，６ａ，６ｂ，７ａ，７ｂ，８
ａ，８ｂを経由して４塔の陰イオン交換樹脂塔５〜８内
のＣｒ（VI）含有残液はバルブ５ｃ，５ｄ，６ｃ，６
ｄ，７ｃ，７ｄ，８ｃ，８ｄを通り更にバルブ３ｂを介
して空の第３の再生液タンク３に入る。Then, the valve 10a of the air 10 is opened, and the valves 5a, 5b, 6a, 6b, 7a, 7b, 8
The residual liquids containing Cr (VI) in the four anion exchange resin towers 5 to 8 are passed through valves a, b and c via valves a and b.
After passing through d, 7c, 7d, 8c and 8d, it enters the empty third regenerating liquid tank 3 via the valve 3b.
【００２２】更に水１１のバルブ１１ａが開き、バルブ
５ａ，５ｂ，６ａ，６ｂ，７ａ，７ｂ，８ａ，８ｂを経
由して４塔の陰イオン交換樹脂塔５〜８内の陰イオン交
換樹脂の表面に付着したＣｒ（VI）液をバルブ５ｃ，５
ｄ，６ｃ，６ｄ，７ｃ，７ｄ，８ｃ，８ｄを通り更にバ
ルブ３ｂを介して第３の再生液タンク３に入る。その後
第３の再生液タンク３には苛性ソーダ溶液９がバルブ９
ａを介して所定量添加され濃度調整される。これまでの
作業で向流多段再生工程は終了となり、以後は例えば、
その位置で水洗を行うか、或いはイオン交換塔上部、下
部のバルブ５ｂ，５ｃ，６ｂ，６ｃ，７ｂ，７ｃ，８
ｂ，８ｃを脱着して別の場所で水洗をおこなうことにな
る。Further, the valve 11a of the water 11 is opened, and the anion exchange resin in the four anion exchange resin towers 5 to 8 is passed through the valves 5a, 5b, 6a, 6b, 7a, 7b, 8a and 8b. The Cr (VI) liquid adhering to the surface is removed from the valves 5c and 5
After passing through d, 6c, 6d, 7c, 7d, 8c, 8d, it enters the third regenerating liquid tank 3 via the valve 3b. Thereafter, a caustic soda solution 9 is supplied to the third regenerating liquid tank 3 with a valve 9.
A predetermined amount is added via a to adjust the concentration. Up to now, the countercurrent multistage regeneration process has been completed, and thereafter, for example,
Water washing is performed at that position, or the valves 5b, 5c, 6b, 6c, 7b, 7c, 8 at the upper and lower portions of the ion exchange tower.
The b and 8c are detached and washed at another place.
【００２３】なお、すでに述べたように、第１の再生タ
ンク１の液をＣｒ（VI）濃厚液タンク４に入れるか、回
収液タンク１２に回収するか、その液量をどのように調
節するかは、陰イオン交換塔の樹脂に吸着したＣｒ（V
I）に依存し、ケースバイケースとなる。また、その切
り替えは、Ｃｒ（VI）濃厚液タンク４内のＣｒ（VI）濃
厚液をどの程度使用したか（イオン交換塔にどの程度の
量を通液したか）を検知手段で検知し、記憶しておき、
この量だけ第１の再生タンク１の液をＣｒ（VI）濃厚液
タンク４に入れ、その後バルブなどのオンオフを切り替
えて、回収液タンク１２似いれるという操作を自動的に
行うようにしても良い。As described above, whether the liquid in the first regenerating tank 1 is put in the Cr (VI) concentrated liquid tank 4 or collected in the collected liquid tank 12, and how the liquid amount is adjusted. The amount of Cr (V
Depends on I) and is case by case. The switching is performed by detecting how much the Cr (VI) concentrated liquid in the Cr (VI) concentrated liquid tank 4 has been used (how much liquid has passed through the ion exchange tower) by the detecting means. Remember,
This amount of the liquid in the first regeneration tank 1 may be charged into the Cr (VI) concentrated liquid tank 4, and then the valve may be switched on and off to automatically perform an operation similar to the recovery liquid tank 12. .
【００２４】参考までに本発明方法により得られた回収
液タンク１２の組成及び濃度の一例を従来法と共に下記
表１に示す。For reference, an example of the composition and concentration of the recovered liquid tank 12 obtained by the method of the present invention is shown in Table 1 below together with the conventional method.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【発明の効果】本発明を実施することにより、需要家で
使用済みの陰イオン交換樹脂塔からＣｒ（VI）を高濃度
でかつ不純物の少ない状態で回収することが可能にな
る。According to the present invention, it is possible to recover Cr (VI) from an anion exchange resin tower used by a customer in a high concentration and with few impurities.
【図１】本発明に係るＣｒ（VI）の高濃度回収法の説明
図。FIG. 1 is an explanatory diagram of a method for recovering a high concentration of Cr (VI) according to the present invention.
１〜３…第1〜第３の再生液タンク 1a，1b，2a，2b，3a，3b，4a，4b，5a〜5d，6a〜6d，7a
〜7d，8a〜8d，9a，10a，11a，12a，13a，16a．．．バ
ルブ ４…Ｃｒ（VI）濃厚液タンク、 ５〜８…陰イオン交換樹脂塔、 ９…苛性ソーダ溶液、 １０…エアー、 １１…水、 １２…回収液タンク、 １３，１４…ポンプ １５．．．硫酸溶液 １６．．．排水 １７．．．再生スタンド1-3: first to third regenerating liquid tanks 1a, 1b, 2a, 2b, 3a, 3b, 4a, 4b, 5a to 5d, 6a to 6d, 7a
~ 7d, 8a ~ 8d, 9a, 10a, 11a, 12a, 13a, 16a. . . Valve 4: Cr (VI) concentrated liquid tank, 5-8: Anion exchange resin tower, 9: Caustic soda solution, 10: Air, 11: Water, 12: Recovered liquid tank, 13, 14: Pump 15. . . Sulfuric acid solution 16. . . Drainage 17. . . Play stand
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０２Ｆ 1/42 Ｃ０２Ｆ 1/42 Ｂ (72)発明者 今津 英幸 福島県郡山市日和田町字小堰26番地 日本 電工株式会社郡山工場内 Ｆターム(参考） 4D017 AA01 BA13 CA17 DA01 DB10 EA01 4D025 AA09 AB21 BA15 BB08 DA10──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) C02F 1/42 C02F 1/42 B (72) Inventor Hideyuki Imazu 26 Koizumi, Hiwadacho, Koriyama-shi, Fukushima Prefecture Address Japan Electric Works Co., Ltd. Koriyama Plant F-term (reference) 4D017 AA01 BA13 CA17 DA01 DB10 EA01 4D025 AA09 AB21 BA15 BB08 DA10
Claims (4)
Ｃｌ- イオンを飽和吸着した陰イオン交換樹脂塔に、Ｃ
ｒ（VI）濃厚液を通液してＳＯ4 2- 、Ｃｌ-イオンを押
し出す工程と、この工程の後、向流多段再生法を行なっ
てＣｒ（VI）のみを高濃度で回収する工程とを有するこ
とを特徴とするＣｒ（VI）の回収方法。1. An anion exchange resin tower in which at least Cr (VI), SO 4 2− and Cl − ions are saturated and adsorbed,
passing a concentrated solution of r (VI) to extrude SO 4 2− and Cl − ions, and, after this step, recovering only Cr (VI) at a high concentration by performing a countercurrent multistage regeneration method. A method for recovering Cr (VI), comprising:
段再生法で回収した液を再利用することを特徴とする請
求項１に記載のＣｒ（VI）の回収方法。2. The method for recovering Cr (VI) according to claim 1, wherein the liquid having a high concentration of Cr (VI) passed through is reused by recovering the liquid recovered by the countercurrent multistage regeneration method.
て同時再生することを特徴とする請求項１に記載のＣｒ
（VI）の回収方法。3. The Cr according to claim 1, wherein the regeneration is performed by simultaneously arranging a plurality of ion exchange towers in parallel.
(VI) Recovery method.
- イオンを飽和吸着した陰イオン交換樹脂塔を充填した
イオン交換塔と、このイオン交換塔内のイオン交換樹脂
を再生するための再生液を充填した向流多段再生法を行
うための複数の再生液タンクと、第１の再生液タンクか
らイオン交換塔に通液して得られた液を入れるＣｒ（V
I）高濃度液タンク及び回収液タンクとを具備したＣｒ
（VI）の回収装置。4. At least Cr (VI), SO 4 2− , Cl
- an ion exchange column was packed with an anion exchange resin column was saturated adsorption ions, a plurality of reproduction for performing countercurrent multistage regeneration process filled with regenerant for regenerating the ion exchange resin of the ion exchange tower Liquid and a liquid containing the liquid obtained by passing the liquid from the first regenerating liquid tank to the ion exchange tower.
I) Cr with high concentration liquid tank and recovery liquid tank
(VI) recovery equipment.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000268913A JP3993370B2 (en) | 2000-09-05 | 2000-09-05 | Method for recovering Cr (V1) from anion exchange resin tower |
| KR10-2001-0053918A KR100432132B1 (en) | 2000-09-05 | 2001-09-03 | Method Of Collecting Cr(Ⅵ) From Anion Exchange Resin and Collecting Apparatus |
| TW090121806A TW576753B (en) | 2000-09-05 | 2001-09-04 | Method of collection Cr(VI) from anion exchange resin column and collecting apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000268913A JP3993370B2 (en) | 2000-09-05 | 2000-09-05 | Method for recovering Cr (V1) from anion exchange resin tower |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002079115A true JP2002079115A (en) | 2002-03-19 |
| JP3993370B2 JP3993370B2 (en) | 2007-10-17 |
Family
ID=18755613
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000268913A Expired - Fee Related JP3993370B2 (en) | 2000-09-05 | 2000-09-05 | Method for recovering Cr (V1) from anion exchange resin tower |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3993370B2 (en) |
| KR (1) | KR100432132B1 (en) |
| TW (1) | TW576753B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015174048A (en) * | 2014-03-17 | 2015-10-05 | 株式会社三進製作所 | Ion exchange resin tower and method for regenerating ion exchange resin |
| JP2015174047A (en) * | 2014-03-17 | 2015-10-05 | 株式会社三進製作所 | Ion exchange resin regenerator and ion exchange resin regeneration system |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100509250B1 (en) * | 2002-10-15 | 2005-08-23 | 삼원금속 주식회사 | Apparatus for recovering sexivalent chrome in chromium plating washing water and method thereof |
-
2000
- 2000-09-05 JP JP2000268913A patent/JP3993370B2/en not_active Expired - Fee Related
-
2001
- 2001-09-03 KR KR10-2001-0053918A patent/KR100432132B1/en not_active IP Right Cessation
- 2001-09-04 TW TW090121806A patent/TW576753B/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015174048A (en) * | 2014-03-17 | 2015-10-05 | 株式会社三進製作所 | Ion exchange resin tower and method for regenerating ion exchange resin |
| JP2015174047A (en) * | 2014-03-17 | 2015-10-05 | 株式会社三進製作所 | Ion exchange resin regenerator and ion exchange resin regeneration system |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100432132B1 (en) | 2004-05-17 |
| KR20020019396A (en) | 2002-03-12 |
| JP3993370B2 (en) | 2007-10-17 |
| TW576753B (en) | 2004-02-21 |
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