JPH08144100A - Separation, concentration and recovery of acid from waste acid etching liquid of aluminum - Google Patents
Separation, concentration and recovery of acid from waste acid etching liquid of aluminumInfo
- Publication number
- JPH08144100A JPH08144100A JP30683894A JP30683894A JPH08144100A JP H08144100 A JPH08144100 A JP H08144100A JP 30683894 A JP30683894 A JP 30683894A JP 30683894 A JP30683894 A JP 30683894A JP H08144100 A JPH08144100 A JP H08144100A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- acid
- exchange membrane
- waste liquid
- hydrogen ions
- 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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Links
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- Water Treatment By Electricity Or Magnetism (AREA)
- ing And Chemical Polishing (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えばアルミニウムを
硫酸又はこれを主成分とする水溶液により陽極酸化処理
をした後、排出される廃液中から硫酸を分離して濃縮・
回収するなどのアルミニウムの酸エッチング廃液からの
酸の分離濃縮回収方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a method in which, for example, aluminum is subjected to anodizing treatment with sulfuric acid or an aqueous solution containing it as a main component, and then sulfuric acid is separated from the waste liquid discharged and concentrated.
The present invention relates to a method for separating, concentrating and recovering an acid from an acid etching waste liquid of aluminum such as recovering.
【０００２】[0002]
【従来の技術】アルミニウムは航空機、船舶、車両、各
種機械の部品、建築材としてのサッシやカ−テンウォ−
ルをはじめ、電気製品、事務用品その他の各種分野で使
用されているが、従来、その耐食性を改善するためにそ
のアルミニウムに陽極酸化処理を施こすことにより、表
面に耐食性の酸化皮膜を形成することが広く行われてお
り、この陽極酸化処理は良質の皮膜が比較的小さい処理
コストで形成できることから、多くの場合硫酸或いは硫
酸を主体とする電解浴が使用されている。2. Description of the Related Art Aluminum is used for parts of aircrafts, ships, vehicles, various machines, sashes and curtains as construction materials.
, It is used in various fields such as electric appliances, office supplies and others. Conventionally, aluminum is subjected to anodizing treatment to improve its corrosion resistance, thereby forming a corrosion resistant oxide film on the surface. In this anodizing treatment, a high-quality film can be formed at a relatively low treatment cost, so that sulfuric acid or an electrolytic bath mainly containing sulfuric acid is often used.
【０００３】ところが、そのように硫酸陽極酸化処理に
より酸化皮膜を形成する場合、同じ処理液で長時間その
処理を行っていると、被陽極酸化材であるアルミニウム
が電解浴中に硫酸アルミニウムとして僅かずつ溶解・蓄
積し、このため電解浴中の遊離硫酸濃度が次第に減少し
てくる。電解浴がこのようになると、アルミニウム表面
に形成される酸化皮膜に緻密性がなくなるなどの悪影響
を与えることから、従来硫酸陽極酸化処理においては、
電解浴中になお有効な硫酸が含まれているにも拘わら
ず、これを廃液として廃棄せざるを得なかった。However, when an oxide film is formed by such sulfuric acid anodic oxidation treatment, if the same treatment liquid is used for a long time, aluminum as an anodized material is slightly converted into aluminum sulfate as aluminum sulfate. The free sulfuric acid concentration in the electrolytic bath gradually decreases. If the electrolytic bath becomes like this, it adversely affects the oxide film formed on the aluminum surface, such as lack of denseness. Therefore, in the conventional sulfuric acid anodizing treatment,
Despite the fact that the electrolytic bath still contained valid sulfuric acid, it had to be discarded as a waste liquid.
【０００４】しかし、このような廃液をそのまま廃棄す
ると、単に硫酸の損失となるばかりでなく、公害上の問
題があり、このためその廃液を大量のアルカリにより中
和するなどの処理が要求され、その無害化処理や廃棄に
多大の費用を要していたが、これらの問題を解決する手
法の一つとして、これまで陰イオン交換膜による電気を
負荷しない拡散透析法を用いる手法が提案されている。However, if such a waste liquid is discarded as it is, not only the sulfuric acid is lost but there is a problem of pollution. Therefore, a treatment such as neutralizing the waste liquid with a large amount of alkali is required, The detoxification treatment and disposal required a great deal of money, but as one of the methods for solving these problems, a method using a diffusion dialysis method that does not load electricity with an anion exchange membrane has been proposed so far. There is.
【０００５】例えば、特公昭５３−７９１８号公報に記
載の方法によれば、硫酸によるアルミニウムの陽極酸化
処理廃液を陰イオン交換膜を介して水と対置して透析さ
せ、上記廃液中の硫酸を水側に選択的且つ効率的に分離
回収するというものであり、この方法ではこの処理を所
定の操作条件下すなわち１０ｇ／ｌ以上の濃度のアルミ
ニウムの存在下に行うことにより硫酸の透析量を飛躍的
に増大させ、その廃液中に存在する遊離硫酸を７０％以
上もの高率で回収できるというものである。For example, according to the method disclosed in Japanese Examined Patent Publication No. 53-7918, the waste liquid of the anodizing treatment of aluminum with sulfuric acid is dialyzed by being placed against water through an anion exchange membrane to remove the sulfuric acid in the waste liquid. This method is to selectively and efficiently separate and recover the water side. In this method, this treatment is performed under predetermined operating conditions, that is, in the presence of aluminum having a concentration of 10 g / l or more, so that the dialysis amount of sulfuric acid is significantly increased. The free sulfuric acid present in the waste liquid can be recovered at a high rate of 70% or more.
【０００６】しかしこの廃液処理法は、その廃液から硫
酸を回収することを目的とするものではあるが、この方
法の場合、回収される硫酸は回収側に水を使用し、廃液
との濃度差を利用するため、いつの場合にも廃液よりも
低い濃度の硫酸にならざるを得ず、また商業的に効率よ
く実施するためには、処理廃液中１０ｇ／ｌ以上の濃度
のアルミニウムの存在下に行うこと等、所定の前提ない
しは条件が必要不可欠である。However, this waste liquid treatment method aims at recovering sulfuric acid from the waste liquid, but in the case of this method, the sulfuric acid to be recovered uses water on the recovery side and has a difference in concentration from the waste liquid. In order to carry out commercially efficiently, it is necessary to use sulfuric acid having a concentration lower than that of the waste liquid in order to utilize it in the presence of aluminum having a concentration of 10 g / l or more in the treatment waste liquid. Certain prerequisites or conditions, such as what to do, are essential.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、拡散透析法
を適用した従来技術が有する上記のような欠点を有しな
いアルミニウムの陽極酸化処理廃液などのアルミニウム
の酸エッチング廃液からの酸の分離濃縮回収方法を提供
することを目的とするものであり、これを特定のカチオ
ン交換膜と特定のアニオン交換膜とを組み合わせて用い
る電気透析槽を使用する新規な方法を提供する。DISCLOSURE OF THE INVENTION The present invention is to separate and concentrate an acid from an aluminum acid etching waste liquid such as an aluminum anodizing waste liquid which does not have the above-mentioned drawbacks of the prior art to which the diffusion dialysis method is applied. It is an object of the present invention to provide a recovery method, and to provide a novel method using an electrodialysis cell which uses a combination of a specific cation exchange membrane and a specific anion exchange membrane.
【０００８】[0008]
【課題を解決するための手段】すなわち、本発明は、水
素イオンを選択的に透過するカチオン交換膜と水素イオ
ンを透過しにくいアニオン交換膜とを陽極、陰極間に交
互に配列して形成される電気透析槽の脱塩室にアルミニ
ウムの酸エッチング廃液を供給して通電することによ
り、濃縮室から濃縮酸を回収することを特徴とするアル
ミニウムの酸エッチング廃液からの酸の分離濃縮回収方
法である。That is, the present invention is formed by alternately arranging a cation exchange membrane selectively transmitting hydrogen ions and an anion exchange membrane hardly transmitting hydrogen ions between an anode and a cathode. A method for separating, concentrating and recovering an acid from an aluminum acid etching waste liquid, which is characterized in that concentrated acid is recovered from a concentrating chamber by supplying an aluminum acid etching waste liquid to a desalting chamber of an electrodialysis tank and energizing it. is there.
【０００９】ここで、本発明においてその処理対象とす
るアルミニウムの酸エッチング廃液の代表例である前記
アルミニウムの陽極酸化処理廃液とは、アルミニウム又
はアルミニウム合金を硫酸又は硫酸を主体とする電解浴
中で陽極酸化する過程から排出する廃液であり、この廃
液中には陽極酸化処理の被処理材であるアルミニウムか
ら溶出したアルミニウム分が硫酸アルミニウムとして含
有され、また電解浴の主成分として使用されて、まだ有
効な硫酸が通常約５０ｇ／ｌ〜３００ｇ／ｌ程度含有さ
れている。また上記廃液には、電解浴成分としてその中
に添加されたシュウ酸、コハク酸、クロム酸又はそれら
の塩等に起因して、これら成分が若干量含有される場合
があるが、本発明によれば、これら成分を含む廃液につ
いても同様に適用することができるものである。Here, the aluminum anodic oxidation treatment waste liquid, which is a typical example of the aluminum acid etching waste liquid to be treated in the present invention, means aluminum or aluminum alloy in sulfuric acid or an electrolytic bath mainly containing sulfuric acid. It is a waste liquid discharged from the process of anodizing.In this waste liquid, the aluminum component eluted from the aluminum that is the material to be anodized is contained as aluminum sulfate, and is also used as the main component of the electrolytic bath. Effective sulfuric acid is usually contained in an amount of about 50 to 300 g / l. Further, the waste liquid may contain a small amount of these components due to oxalic acid, succinic acid, chromic acid or salts thereof added as an electrolytic bath component, but the present invention According to this, the same can be applied to the waste liquid containing these components.
【００１０】また、上記水素イオンを選択的に透過する
カチオン交換膜としては、水素イオンを選択的に透過す
る性能を備えたカチオン交換膜であれば特に限定はない
が、その一例として、好ましくは特開平５−２２８３４
４号公報に記載のカチオン交換膜を挙げることができ
る。ここに記載のカチオン交換膜は、陰イオン交換体層
と陽イオン交換体層とを一体化した複層イオン交換膜
を、好ましくは陰イオン交換体層を陽極側に面するよう
に使用し、これにより水素イオンの透過性を大きくし、
他の陽イオンの透過性を可及的に小さくすることができ
る。The cation exchange membrane that selectively permeates hydrogen ions is not particularly limited as long as it is a cation exchange membrane having the ability to selectively permeate hydrogen ions, but as an example, it is preferable. JP-A-5-22834
The cation exchange membrane described in Japanese Patent No. 4 can be mentioned. The cation exchange membrane described here is a multilayer ion exchange membrane in which an anion exchanger layer and a cation exchanger layer are integrated, preferably used so that the anion exchanger layer faces the anode side, This increases the permeability of hydrogen ions,
The permeability of other cations can be made as small as possible.
【００１１】ここで上記複層イオン交換膜を構成するそ
の陰イオン交換体層としては、好ましくは実質的に芳香
族環と連結基から構成されたセグメントであって、陰イ
オン交換基が導入されたセグメントと陰イオン交換基が
実質的に導入されていないセグメントとのブロック共重
合体が使用され、また上記複層イオン交換膜を構成する
その陽イオン交換体層としては、好ましくはスチレン又
はその誘導体とジビニルベンゼンとの共重合体を母体と
する強酸性陽イオン交換膜が用いられる。また、これら
両者を一体化した複層イオン交換膜は、好ましくは膜状
に成形された陽イオン交換体層に、陰イオン交換体層を
形成する重合体溶液を流延、乾燥し、積層させて得られ
る。The anion-exchanger layer constituting the multi-layered ion-exchange membrane is preferably a segment substantially composed of an aromatic ring and a linking group, and an anion-exchange group is introduced therein. A block copolymer of a segment and a segment in which an anion exchange group is not substantially introduced is used, and the cation exchanger layer constituting the multilayer ion exchange membrane is preferably styrene or A strongly acidic cation exchange membrane having a copolymer of the derivative and divinylbenzene as a matrix is used. In addition, the multilayer ion exchange membrane integrating both of these is preferably a membrane-shaped cation exchanger layer, a polymer solution for forming an anion exchanger layer is cast, dried and laminated. Obtained.
【００１２】この複層イオン交換膜においては、水素イ
オンの場合、陽イオン交換体層だけでは水素イオンとと
もにアルミニウムイオンも透過してしまい、所期の透析
効果が得られないため、その表面に陰イオン交換膜を積
層させた複層構造とし、これによりイオン半径の大きい
アルミニウムイオンの透過を阻止し、水素イオンを選択
的に透過させるようにしたものである。In this multi-layered ion exchange membrane, in the case of hydrogen ions, aluminum ions as well as hydrogen ions permeate only by the cation exchanger layer, and the desired dialysis effect cannot be obtained. It has a multi-layered structure in which ion exchange membranes are laminated, whereby aluminum ions having a large ionic radius are prevented from permeating, and hydrogen ions are selectively permeated.
【００１３】なかでもイオン交換容量０．５〜４ミリ当
量／ｇ乾燥樹脂、固定イオン濃度１〜１０ミリ当量／ｇ
Ｈ2Ｏ、膜厚０．１〜１５０μｍ及び硫酸０．５モル／
リットル溶液中の抵抗が１Ω・ｃｍ2 以下を有する陽極
側の陰イオン交換体層と陰極側の陽イオン交換体層との
複層イオン交換膜として構成することにより、水素イオ
ン選択透過性が高く、水分裂を生じる限界電流密度が高
い膜として使用することができる。Among them, the ion exchange capacity is 0.5 to 4 meq / g dry resin, and the fixed ion concentration is 1 to 10 meq / g.
H 2 O, film thickness 0.1 to 150 μm and sulfuric acid 0.5 mol /
Highly selective permeation of hydrogen ions is obtained by constituting a multi-layer ion exchange membrane consisting of an anion exchange layer on the anode side and a cation exchange layer on the cathode side having a resistance of 1 Ω · cm 2 or less in a liter solution. It can be used as a membrane with high limiting current density that causes water splitting.
【００１４】また、本発明では、上記水素イオンを選択
的に透過するカチオン交換膜とともに、水素イオンを透
過しにくいアニオン交換膜を組合わせて使用し、これに
より廃液中の硫酸イオンをそのイオン交換作用により、
選択的にアニオン交換膜を透過、移行させるが、このア
ニオン交換膜としては、通常の強塩基性アニオン交換膜
ではなく、好ましくは３級アミンなどの弱塩基性のアニ
オン交換基を有するアニオン膜などの水素イオンを透過
しにくいアニオン交換膜であれば何れも使用することが
でき、またそのような特性を有するものであれば、均一
系や不均一系、また縮合系や重合系を問わず使用するこ
とができる。In the present invention, a cation exchange membrane that selectively permeates hydrogen ions is used in combination with an anion exchange membrane that does not easily permeate hydrogen ions, whereby the sulfate ions in the waste liquid are exchanged by the ion exchange membrane. By the action
Although it selectively permeates and migrates through the anion exchange membrane, this anion exchange membrane is not an ordinary strongly basic anion exchange membrane, but preferably an anion membrane having a weakly basic anion exchange group such as a tertiary amine. Any anion exchange membrane that does not easily permeate hydrogen ions can be used, and if it has such characteristics, it can be used regardless of whether it is a homogeneous system or a heterogeneous system, or a condensation system or a polymerization system. can do.
【００１５】図１は、本発明の分離濃縮回収方法を実施
する電気透析装置の一態様を示す概略図である。図１
中、１は容器、２は陽極、３は陰極であり、また４は陽
極室、５は陰極室である。またＨは水素イオンを選択的
に透過するカチオン交換膜、Ａは水素イオンを透過しに
くいアニオン交換膜であり、図示のとおり、水素イオン
を選択的に透過するカチオン交換膜Ｈ及び水素イオンを
透過しにくいアニオン交換膜Ａの複数個が相対して所定
間隔を置いて交互に配列されている。FIG. 1 is a schematic view showing an embodiment of an electrodialysis apparatus for carrying out the method of separation, concentration and recovery according to the present invention. FIG.
Inside, 1 is a container, 2 is an anode, 3 is a cathode, 4 is an anode chamber, and 5 is a cathode chamber. Further, H is a cation exchange membrane that selectively permeates hydrogen ions, and A is an anion exchange membrane that does not easily permeate hydrogen ions. A plurality of anion exchange membranes A that are difficult to perform are alternately arranged at a predetermined interval in opposition to each other.
【００１６】そして上記配列により、陽極２側がアニオ
ン交換膜Ａで、陰極３側がカチオン交換膜Ｈで区画され
た複数個の区画室すなわち脱塩室Ｓ1、Ｓ2・・・Ｓｎ
（これらの各区画室に被処理廃液が供給される）と、陽
極２側がカチオン交換膜Ｈで、陰極３側がアニオン交換
膜Ａで区画された複数個の区画室すなわち濃縮室Ｔ1、
Ｔ2・・・Ｔｎとが交互に構成されている。With the above arrangement, a plurality of compartments, that is, deionization compartments S 1 , S 2 ... Sn are defined by the anion exchange membrane A on the anode 2 side and the cation exchange membrane H on the cathode 3 side.
(Waste liquid to be treated is supplied to each of these compartments), a plurality of compartments in which the anode 2 side is the cation exchange membrane H and the cathode 3 side is the anion exchange membrane A, that is, the concentrating chamber T 1 ,
T 2 ... Tn are alternately configured.
【００１７】また、陽極室４は、カチオン交換膜Ｈ及び
容器１の内壁により区画されて構成され、図示のとおり
その中に陽極２が配置され、また陰極室５は、カチオン
交換膜Ｈ及び容器１の内壁により区画されて構成され、
その中に陽極２が配置されている。また図１中、６は脱
塩室Ｓ1、Ｓ2・・・Ｓｎへの被処理液供給用の導管であ
り、７は濃縮室Ｔ1、Ｔ2・・・Ｔｎへの回収液供給用の
導管である。Further, the anode chamber 4 is constituted by being partitioned by the cation exchange membrane H and the inner wall of the container 1, the anode 2 is disposed therein as shown in the drawing, and the cathode chamber 5 is constituted by the cation exchange membrane H and the container. It is configured by being divided by the inner wall of 1.
The anode 2 is arranged therein. In FIG. 1, 6 is a conduit for supplying the liquid to be treated to the demineralization chambers S 1 , S 2 ... Sn, and 7 is a liquid for supplying the recovery liquid to the concentration chambers T 1 , T 2 ... Tn. Is the conduit of.
【００１８】以上は、この態様における基本的構成であ
るが（なお、ここでその区画室が１個の場合には、全体
として３室構造となる）、これらの構成を備えている限
り、フィルタ−プレス型（圧濾器型）やユニットセル型
（水槽型）の何れでも適用可能である。なお図１中被処
理液及び回収液の排出用の導管は図示していないが、こ
れは必要に応じて回分形式（バッチ式）、循環形式の何
れも採用することができる。また被処理液と回収液とは
図１に示した態様では並流形式であるが、これとは逆に
両液流を対流（向流）形式とすることもきることは勿論
である。The above is the basic configuration in this embodiment (note that, when the number of compartments is one, the overall structure is three chambers), but as long as these configurations are provided, the filter is provided. -A press type (pressurizer type) or a unit cell type (water tank type) is applicable. Although the conduits for discharging the liquid to be treated and the recovered liquid are not shown in FIG. 1, any of a batch system (circulation system) and a circulation system can be adopted as necessary. Further, although the liquid to be treated and the recovered liquid are of the parallel flow type in the embodiment shown in FIG. 1, it is needless to say that both liquid flows may be of the convection type (countercurrent type).
【００１９】この装置の操作に際しては、両電極２及び
３間に所定の電圧がかけられる。また区画室（脱塩室）
Ｓ1、Ｓ2・・・Ｓｎに対し、本発明における処理対象液
である例えば硫酸によるアルミニウムの陽極酸化処理廃
液が導管６を介して好ましくは１〜２０ｃｍ／秒の流速
で供給され、一方区画室（濃縮室）Ｔ1、Ｔ2・・・Ｔｎ
には、回収液すなわち水又は適宜の電解質を含む水溶
液、例えば硫酸水溶液が好ましくは１〜２０ｃｍ／秒の
流速で供給される。また両電極室４及び５の電解質溶液
としては、電流を有効に通すものであれば差し支えな
く、適宜の溶液を使用するが、区画室（濃縮室）Ｔ1、
Ｔ2・・・Ｔｎへ供給する水溶液と同じ溶液を使用する
こともできる。When operating this device, a predetermined voltage is applied between the electrodes 2 and 3. Separated room (demineralization room)
For S 1 , S 2 ... Sn, the waste liquid of the anodizing treatment of aluminum with sulfuric acid, which is the liquid to be treated in the present invention, is supplied through conduit 6 at a flow rate of preferably 1 to 20 cm / sec, and one compartment Chambers (concentration chambers) T 1 , T 2 ... Tn
In this case, a recovery liquid, that is, water or an aqueous solution containing an appropriate electrolyte, for example, a sulfuric acid aqueous solution is preferably supplied at a flow rate of 1 to 20 cm / sec. As the electrolyte solution of both the electrode compartments 4 and 5, no harm as long as it passes the current effective, but using an appropriate solution, compartment (concentrating compartment) T 1,
It is also possible to use the same solution as the aqueous solution supplied to T 2 ... Tn.
【００２０】以上の操作中、被処理液中の硫酸イオン
（ＳＯ4 2- ）成分は、これと反対の電荷を有する電極
（＋極）方向へ移動し、水素イオンを拡散透過しにくい
アニオン交換膜Ａを通して区画室（濃縮室）Ｔ1、Ｔ2・
・・Ｔｎへ透過移行し、また被処理液中の水素イオンは
これと反対の電荷を有する電極（−極）方向へ移動し、
水素イオンを選択的に透過するカチオン交換膜Ｈを通し
て同じく区画室（濃縮室）Ｔ1、Ｔ2・・・Ｔｎへ透過移
行し、区画室（濃縮室）Ｔ1、Ｔ2・・・Ｔｎ中の回収液
へ硫酸分として濃縮回収される。During the above operation, the sulfate ion (SO 4 2− ) component in the liquid to be treated moves toward the electrode (+ electrode) having the opposite electric charge to the anion exchange which is difficult to diffuse and permeate hydrogen ions. Compartments (concentration chambers) T 1 , T 2 · through membrane A
..Transmitting to Tn, hydrogen ions in the liquid to be treated move toward the electrode (-pole) having the opposite electric charge,
Similarly compartment through the cation exchange membrane H which selectively transmits hydrogen ions (concentration chamber) T 1, T 2 ··· to Tn and transmission shifts, compartment (concentrating compartment) T 1, T 2 ··· Tn in Sulfuric acid is concentrated and recovered in the recovery solution of.
【００２１】このとき被処理液中の水素イオンは、水素
イオンを選択的に透過するカチオン交換膜Ｈを通過する
が、アルミニウムイオン（Ａｌ3+）は通過しない。図１
で云えば、アルミニウムイオン（Ａｌ3+）は脱塩室
Ｓ1、Ｓ2・・・Ｓｎ中の被処理液中にそのまま残り、被
処理液は硫酸が除去されるに従って液量の減少が起こ
り、これが結果として被処理液中で濃縮され、高濃度の
硫酸アルミニウムとして得ることができるものである。At this time, the hydrogen ions in the liquid to be treated pass through the cation exchange membrane H which selectively permeates the hydrogen ions, but not the aluminum ions (Al 3+ ). FIG.
Speaking of which, aluminum ions (Al 3+ ) remain in the liquid to be treated in the desalting chambers S 1 , S 2 ... Sn, and the amount of the liquid to be treated decreases as sulfuric acid is removed. As a result, this is concentrated in the liquid to be treated and can be obtained as high-concentration aluminum sulfate.
【００２２】また、上記操作中すなわち通電処理時に透
析装置に印加する電圧は、好ましくは０．１〜１．０Ｖ
（ボルト）／陰陽膜単位程度であり、電流密度は好まし
くは１〜２０Ａ／ｄｍ2 程度であるが、これら範囲とは
限らず、被処理廃液中の硫酸及び硫酸アルミニウムの各
濃度、使用する交換膜Ｈ及びＡの種類、また電気透析装
置の規模等如何により適宜設定することができる。以上
は、アルミニウムの硫酸による陽極酸化廃液を例にして
説明したが、本発明はアルミニウムの塩酸、修酸、硝酸
などによる酸エッチング廃液にも同様にして適用でき、
この場合にはこれらの各酸に対応するアルミニウム塩を
高濃度で得ることができる。The voltage applied to the dialyzer during the above operation, that is, during the energization treatment, is preferably 0.1 to 1.0 V.
(Volts) / Yin-Yo membrane unit, and the current density is preferably about 1 to 20 A / dm 2 , but not limited to these ranges, each concentration of sulfuric acid and aluminum sulfate in the waste liquid to be treated, and exchange used. It can be appropriately set depending on the types of the membranes H and A and the scale of the electrodialysis device. The above is described by taking the anodizing waste liquid of aluminum sulfuric acid as an example, but the present invention can be similarly applied to the acid etching waste liquid of aluminum hydrochloric acid, oxalic acid, nitric acid, etc.
In this case, the aluminum salt corresponding to each of these acids can be obtained at a high concentration.
【００２３】[0023]
【実施例】以下、本発明を実施例によって説明するが、
かかる実施例によって本発明が制限されるものではない
ことは勿論である。水素イオン選択透過性カチオン交換
膜「セレミオンＨＳＶ」〔旭硝子（株）社製、商品名、
陽イオン交換体層と陰イオン交換体層との複層イオン交
換膜〕と水素イオン難透過性アニオン交換膜「セレミオ
ンＡＡＶ」〔旭硝子（株）社製、商品名、ビニルピリジ
ン系弱塩基性陰イオン交換体膜〕とを上記カチオン交換
膜の複層イオン交換膜の陰イオン交換体層が陽極側に面
するように交互に配列し（図１参照）、カチオン交換膜
の陽極側に構成される脱塩室を１０室及び濃縮室１０室
を有する全有効膜面積が１７．２ｄｍ2 となる電気透析
槽を準備した。EXAMPLES The present invention will be described below with reference to examples.
Of course, the present invention is not limited to the embodiments. Hydrogen ion selective permeable cation exchange membrane "Selemion HSV" [trade name, manufactured by Asahi Glass Co., Ltd.
[Multilayer ion exchange membrane of cation exchanger layer and anion exchanger layer] and hydrogen ion impermeable permeation anion exchange membrane "Selemion AAV" [Asahi Glass Co., Ltd., trade name, vinylpyridine-based weakly basic anion] And an ion exchange membrane] are alternately arranged so that the anion exchange layer of the multilayer ion exchange membrane of the above cation exchange membrane faces the anode side (see FIG. 1), and is formed on the anode side of the cation exchange membrane. An electrodialysis tank having 10 desalting chambers and 10 concentrating chambers with a total effective membrane area of 17.2 dm 2 was prepared.
【００２４】上記電気透析槽の脱塩室には、初期組成と
して、硫酸１９０ｇ／ｌ及び硫酸アルミニウム１８ｇ／
ｌ（Ａｌとして換算）に調整した原液１０リットルを膜
面線速度８ｃｍ／ｓｅｃで循環供給し、濃縮室には２５
０ｇ／ｌの硫酸溶液を満液となる量（１５０ミリリット
ル）張り込んだ。また電気透析槽の両端の電極室には２
００ｇ／ｌの硫酸水溶液を５リットル調整し、循環供給
した。The desalting chamber of the electrodialysis tank had an initial composition of 190 g / l of sulfuric acid and 18 g / aluminum sulfate.
10 liters of the stock solution adjusted to 1 (calculated as Al) were circulated and supplied at a linear velocity of the membrane surface of 8 cm / sec, and 25
A 0 g / l sulfuric acid solution was added to fill up (150 ml). There are two electrode chambers at both ends of the electrodialysis tank.
5 liters of a 00 g / l sulfuric acid aqueous solution was prepared and circulated and supplied.
【００２５】この状態において、０．５ボルト／単位セ
ルで通電したところ、初期には７．０Ａ／ｄｍ2 の電流
が流れ、濃縮室からは３９１ｍｌ／時間で２６９ｇ／ｌ
の硫酸濃縮液が採取された。また同じ０．５ボルト／単
位セルでの通電を１７時間継続したところ、濃縮室から
の溢流液は初めのものを含めて計６．０リットルとな
り、この液の組成は硫酸２５０ｇ／ｌ、硫酸アルミニウ
ム０．１１８ｇ／ｌ（Ａｌとして換算）であった。In this state, when electricity was applied at 0.5 V / unit cell, an electric current of 7.0 A / dm 2 initially flowed, and 391 g / l at 391 ml / hour from the concentrating chamber.
A concentrated sulfuric acid solution was collected. When electricity was continuously applied at the same 0.5 volt / unit cell for 17 hours, the overflow liquid from the concentrating chamber including the first one was 6.0 liters in total, and the composition of this liquid was 250 g / l of sulfuric acid, The amount of aluminum sulfate was 0.118 g / l (calculated as Al).
【００２６】また上記処理終了時の脱塩液の量は４．０
リットルとなっており、組成は硫酸１００ｇ／ｌ、硫酸
アルミニウム４４．８ｇ／ｌ（Ａｌとして換算）であっ
た。またこの間の硫酸の電流効率は４３．９％であっ
た。このように、本発明によれば硫酸等をしかも高濃度
として回収することができ、併わせて高濃度の硫酸アル
ミニウム等を得ることができるものである。The amount of the desalting solution at the end of the above treatment is 4.0.
The composition was 100 g / l of sulfuric acid and 44.8 g / l of aluminum sulfate (calculated as Al). The current efficiency of sulfuric acid during this period was 43.9%. As described above, according to the present invention, sulfuric acid and the like can be recovered in a high concentration and, at the same time, high-concentration aluminum sulfate and the like can be obtained.
【００２７】[0027]
【発明の効果】以上のとおり、本発明によれば、アルミ
ニウムの酸エッチング廃液、例えばアルミニウムの硫酸
による陽極酸化処理廃液から硫酸をアルミニウムイオン
ときわめて有効に分離して濃縮・回収できるとともに、
併わせて高濃度の硫酸アルミニウム等を得ることができ
る。As described above, according to the present invention, sulfuric acid and aluminum ions can be separated and condensed and recovered from an aluminum acid-etching waste liquid, for example, an anodizing waste liquid containing aluminum sulfuric acid, very effectively.
A high concentration of aluminum sulfate or the like can be obtained together.
【図１】本発明方法を実施する電気透析装置の一態様を
示す概略図。FIG. 1 is a schematic view showing one embodiment of an electrodialysis device for carrying out the method of the present invention.
Ｈ 水素イオンを選択的に透過するカチオン交換膜 Ａ 水素イオンを透過しにくいアニオン交換膜 １ 容器 ２、３ 電極 ４ 陽極室 ５ 陰極室 ６ 被処理液供給用導管 ７ 回収液供給用の導管 Ｓ1、Ｓ2・・・Ｓｎ 区画室（脱塩室） Ｔ1、Ｔ2・・・Ｔｎ 区画室（濃縮室）H Cation exchange membrane that selectively permeates hydrogen ions A Anion exchange membrane that is difficult to permeate hydrogen ions 1 Container 2, 3 Electrode 4 Anode chamber 5 Cathode chamber 6 Treated liquid supply conduit 7 Collected liquid supply conduit S 1 , S 2 ... Sn compartment (demineralization room) T 1 , T 2 ... Tn compartment (concentration room)
Claims (4)
換膜と水素イオンを透過しにくいアニオン交換膜とを陽
極、陰極間に交互に配列して形成される電気透析槽の脱
塩室にアルミニウムの酸エッチング廃液を供給して通電
することにより、濃縮室から濃縮酸を回収することを特
徴とするアルミニウムの酸エッチング廃液からの酸の分
離濃縮回収方法。1. Aluminum is provided in a desalting chamber of an electrodialysis tank formed by alternately arranging a cation exchange membrane selectively transmitting hydrogen ions and an anion exchange membrane hardly transmitting hydrogen ions between an anode and a cathode. The method for separating, concentrating and recovering an acid from an acid etching waste liquid of aluminum, characterized in that the concentrated acid is recovered from the concentrating chamber by supplying and energizing the acid etching waste liquid.
ン交換膜が、陰イオン交換体層と陽イオン交換体層との
複合イオン交換膜である請求項１記載のアルミニウムの
酸エッチング廃液からの酸の分離濃縮回収方法。2. The aluminum acid etching waste liquid according to claim 1, wherein the cation exchange membrane selectively permeating hydrogen ions is a composite ion exchange membrane comprising an anion exchange layer and a cation exchange layer. Method for separating, concentrating and recovering acid.
換膜が、弱塩基性アニオン交換膜である請求項１又は２
記載のアルミニウムの酸エッチング廃液からの酸の分離
濃縮回収方法。3. The anion exchange membrane which is difficult to permeate hydrogen ions is a weakly basic anion exchange membrane.
A method for separating, concentrating and recovering an acid from an aluminum acid etching waste liquid as described above.
硫酸による陽極酸化廃液である請求項１、２又は３記載
のアルミニウムの酸エッチング廃液からの酸の分離濃縮
回収方法。4. The aluminum acid etching waste liquid,
The method for separating, concentrating and recovering an acid from an aluminum acid etching waste liquid according to claim 1, which is an anodizing waste liquid with sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30683894A JP3546498B2 (en) | 1994-11-16 | 1994-11-16 | Method for separating, concentrating and recovering acid from aluminum etching wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30683894A JP3546498B2 (en) | 1994-11-16 | 1994-11-16 | Method for separating, concentrating and recovering acid from aluminum etching wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08144100A true JPH08144100A (en) | 1996-06-04 |
| JP3546498B2 JP3546498B2 (en) | 2004-07-28 |
Family
ID=17961872
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30683894A Expired - Lifetime JP3546498B2 (en) | 1994-11-16 | 1994-11-16 | Method for separating, concentrating and recovering acid from aluminum etching wastewater |
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| Country | Link |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003071457A (en) * | 2001-09-04 | 2003-03-11 | Maezawa Ind Inc | Method for recovering mineral acid from mixed acid of boric acid and mineral acid |
| JP2005052794A (en) * | 2003-08-07 | 2005-03-03 | Shigeru Kitani | Method and apparatus for treating aqueous solution |
| WO2009146591A1 (en) * | 2008-06-05 | 2009-12-10 | 佳科太阳能硅(厦门)有限公司 | Recovering treatment method for the waste acid produced in the hydrometallurgical process of silicon |
| JP2010260009A (en) * | 2009-05-08 | 2010-11-18 | Nosaka Denki:Kk | Acid concentrating method |
-
1994
- 1994-11-16 JP JP30683894A patent/JP3546498B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003071457A (en) * | 2001-09-04 | 2003-03-11 | Maezawa Ind Inc | Method for recovering mineral acid from mixed acid of boric acid and mineral acid |
| JP2005052794A (en) * | 2003-08-07 | 2005-03-03 | Shigeru Kitani | Method and apparatus for treating aqueous solution |
| WO2009146591A1 (en) * | 2008-06-05 | 2009-12-10 | 佳科太阳能硅(厦门)有限公司 | Recovering treatment method for the waste acid produced in the hydrometallurgical process of silicon |
| JP2010260009A (en) * | 2009-05-08 | 2010-11-18 | Nosaka Denki:Kk | Acid concentrating method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3546498B2 (en) | 2004-07-28 |
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