JPH06128664A - Method for recovering in - Google Patents
Method for recovering inInfo
- Publication number
- JPH06128664A JPH06128664A JP29913492A JP29913492A JPH06128664A JP H06128664 A JPH06128664 A JP H06128664A JP 29913492 A JP29913492 A JP 29913492A JP 29913492 A JP29913492 A JP 29913492A JP H06128664 A JPH06128664 A JP H06128664A
- Authority
- JP
- Japan
- Prior art keywords
- cement
- solution
- added
- plate
- metal
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、Ｚｎ製錬における中間
物からのＩｎの回収に関し、効率良くしかも有害ガスの
発生を伴わない状態で粗Ｉｎを得る方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to recovery of In from an intermediate in Zn smelting, and relates to a method for efficiently obtaining crude In without producing harmful gas.
【０００２】[0002]
【従来の技術】従来より、Ｉｎは、主として、Ｃｄと共
に、Ｚｎの製錬工程に於ける副産物として産出されるこ
とが知られている。Ｚｎの製錬工程においてＩｎやＣｄ
を分離して行く方法としては、先ず、Ｚｎの製錬工程に
おいて得られる中間物を鉱酸酸性下で還元浸出して、Ｉ
ｎを含有する浸出液を得、次いで、このＩｎを含有する
浸出液に、浸出液中のＩｎ量に対して１化学当量前後の
Ｚｎ粉末もしくはＣｄ−Ｚｎ粉末を添加してセメントＩ
ｎを置換析出させ、さらに、このセメントＩｎにＮａＯ
Ｈを添加して加熱融解し、生成したソーダスラグと粗Ｉ
ｎとを分離回収し、この粗Ｉｎをさらに電解精製して高
純度のＩｎを入手する方法が採られていた。2. Description of the Related Art It has been conventionally known that In is mainly produced as a by-product in the smelting process of Zn together with Cd. In and Cd in Zn smelting process
As a method of separating the iron, first, the intermediate obtained in the smelting process of Zn is subjected to reduction leaching under acidic acid of mineral acid,
A leachate containing n was obtained, and then Zn powder or Cd—Zn powder of about 1 chemical equivalent to the amount of In in the leachate was added to the leachate containing In to obtain the cement I.
n is deposited by substitution, and NaO is added to this cement In.
H was added and melted by heating, soda slag produced and crude I
n was separated and recovered, and the crude In was further electrolytically refined to obtain high-purity In.
【０００３】しかしながら、Ｉｎを含有する浸出液中の
Ｃｄ共存量が多くなると、セメントＩｎ中に占めるＣｄ
の含有量が高くなったり、セメントＩｎを融解する時に
Ｃｄと共存しているＴｅのためにセメントＩｎが酸化し
やすい状態となり、結果的に、粗Ｉｎを高い歩留まりで
収集することが不可能になる等の不都合を生じていた。However, when the coexisting amount of Cd in the leachate containing In increases, the Cd in the cement In will increase.
Content of Cr becomes high, or Te coexists with Cd when cement In is melted, so that cement In is easily oxidized, and as a result, it becomes impossible to collect crude In at a high yield. It caused such inconvenience.
【０００４】特に、浸出液中にＡｓが０．５ｐｐｍ以上
共存する場合には、Ｉｎの置換析出工程で、有害なＡｓ
Ｈ3 の発生を呼び起こしてしまうが、一端ＡｓＨ3 を発
生させると、このＡｓＨ3 の無害化処理が必須とされ、
作業環境等の整備については高額な投資が余儀無くされ
る。Particularly, when As is present in the leachate in an amount of 0.5 ppm or more, the harmful As
It causes the generation of H 3 , but once AsH 3 is generated, the detoxification treatment of AsH 3 is essential,
A large amount of investment will be required to improve the working environment.
【０００５】このため、この投資を軽減させるために、
Ｚｎ粉末もしくはＣｄ−Ｚｎ粉末を添加するに先立ち、
浸出液中のＡｓの含有量を０．５ｐｐｍ未満まで低下さ
せた後、Ｉｎを置換析出させることが一般的であった。Therefore, in order to reduce this investment,
Prior to adding Zn powder or Cd-Zn powder,
It was general that the content of As in the leachate was reduced to less than 0.5 ppm and then In was substituted and precipitated.
【０００６】Ａｓの含有量を低下させる簡便な方法とし
て、イオン交換法や溶媒抽出法が提案されているが、こ
れらの方法にても充分に満足の行くほどＡｓを除去出来
るものではなく、最終的には、硫化処理を施すことによ
りＡｓをＡｓ2 Ｓ3 として固定して分離しなければなら
ない。Ion exchange methods and solvent extraction methods have been proposed as simple methods for reducing the As content, but these methods are not enough to remove As sufficiently, and Specifically, As must be fixed as As 2 S 3 and separated by performing a sulfurating treatment.
【０００７】したがって、イオン交換法や溶媒抽出法の
採用は、Ｉｎの回収工程をより複雑にするばかりでな
く、従来と同様、共存するＣｄも同時に硫化するためＩ
ｎとＣｄの同時回収効率を低くしてしまう。加えて、こ
れらの金属の硫化工程で発生する悪臭を除去することに
多くの配慮を重ねなければならない。Therefore, the adoption of the ion exchange method or the solvent extraction method not only complicates the In recovery process, but also causes coexisting Cd to be sulfided at the same time as in the conventional case.
This lowers the simultaneous recovery efficiency of n and Cd. In addition, much care must be taken in removing the offensive odors generated in the sulfurization process of these metals.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、Ｚｎの製錬
工程で発生する中間物よりＩｎを回収するに際して、従
来にもまして効率的に、しかも、ＡｓＨ3 の発生のない
Ｉｎの回収方法を開示することをその目的とする。DISCLOSURE OF THE INVENTION The present invention is a method of recovering In more efficiently than ever before in recovering In from an intermediate generated in a Zn smelting process, and in which AsH 3 is not generated. The purpose is to disclose.
【０００９】[0009]
【課題を解決するための手段】本発明者等は、上記の課
題を解決するために鋭意研究試験を行った結果、Ｚｎ製
錬工程に於いて発生してくるＣｄ、Ｚｎ、Ｉｎ、Ｔｅ、
Ａｓ等を含有した中間物よりＩｎを回収するに際して、
還元剤としてＴｅ化合物やＡｓ化合物を生成させるに必
要な量の２当量以上の金属Ｃｄと金属Ｉｎもしくはこの
ような量の金属ＣｄとＩｎを含有する還元用澱物を用い
て上記中間物を鉱酸酸性下で還元浸出して浸出液とし、
この浸出液に水酸化アルカリ水溶液を添加してｐＨを
１．５〜２．５に調整し、この液から残渣を分離して得
た濾液中に板状のＣｄを浸漬し、板状のＣｄの表面にセ
メントＩｎを置換析出させ、板状のＣｄの表面より剥離
して得たセメントＩｎに、該セメントＩｎに対して５〜
２０重量％のＮａＯＨを添加して後、摂氏２００〜３０
０度で融解して、発生したソーダスラグを層分解してＩ
ｎを回収すること、さらには、セメントＩｎを置換析出
させた後の尾液に、アルカリ水溶液を添加して、そのｐ
Ｈを４〜６に調整し、生成した沈澱物を中間物の鉱酸酸
性下における還元浸出時に添加することで前記課題の解
決されることを見出し本発明に至ったものである。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, have found that Cd, Zn, In, Te, which are generated in the Zn smelting process,
When recovering In from an intermediate containing As, etc.,
As the reducing agent, the above intermediates are mined using a reducing starch containing 2 or more equivalents of metal Cd and metal In necessary for producing a Te compound or As compound, or a reducing starch containing such amounts of metal Cd and In. Reduced leaching under acidic and acidic conditions to obtain leachate,
Aqueous alkali hydroxide was added to this leachate to adjust the pH to 1.5 to 2.5, and plate-like Cd was immersed in the filtrate obtained by separating the residue from this solution to obtain a plate-like Cd. Cement In obtained by substituting and precipitating cement In on the surface and peeling from the surface of the plate-shaped Cd, and 5 to the cement In
200 to 30 degrees Celsius after adding 20 wt% NaOH
It melts at 0 degrees, and the generated soda slag is decomposed into layers I
n is recovered, and further, an alkaline aqueous solution is added to the tail solution after substitution and precipitation of cement In to add p
The present invention was found to solve the above-mentioned problems by adjusting H to 4 to 6 and adding the formed precipitate during the reduction leaching of the intermediate under acidic acidity of mineral acid.
【００１０】[0010]
【作用】本発明において、Ｚｎ製錬の中間物よりＩｎを
還元浸出させるのは、上記の中間物中に含有されるＴｅ
とＡｓを難溶性のＴｅ化合物とＡｓ化合物とに変じて系
外に除去し易くするためのものであり、この場合、含有
するＴｅとＡｓの２当量をこえる金属ＣｄおよびＩｎを
還元剤として用いているのは、この量が２当量未満では
中間物中に含有されるＴｅとＡｓを難溶性のＴｅ化合物
とＡｓ化合物とに変じるのが不十分であるためである。In the present invention, the reduction leaching of In from the intermediate product of Zn smelting is caused by Te contained in the intermediate product.
And As are converted to a sparingly soluble Te compound and As compound to facilitate removal to the outside of the system. In this case, metal Cd and In exceeding 2 equivalents of Te and As contained are used as a reducing agent. The reason for this is that if this amount is less than 2 equivalents, it is insufficient to transform Te and As contained in the intermediate into a sparingly soluble Te compound and As compound.
【００１１】また、この処理に際して、還元剤の量が２
当量を超える場合には、ＨＣｌやＨ2 ＳＯ4 等の鉱酸酸
性度には特にこだわらない。さらに、還元剤の濃度は５
０〜２００ｇ／リットルとなるように調整することが望
ましい。In this treatment, the amount of reducing agent is 2
When it exceeds the equivalent amount, the acidity of mineral acids such as HCl and H 2 SO 4 is not particularly concerned. Furthermore, the concentration of the reducing agent is 5
It is desirable to adjust it to be 0 to 200 g / liter.
【００１２】なお、上記の中間物中に金属Ｚｎを含有せ
ず、一方、充分な量の金属Ｃｄや金属Ｉｎを含有する場
合には、還元浸出工程として特にこのような還元剤を添
加する必要はない。When the above intermediate does not contain metal Zn but contains a sufficient amount of metal Cd or metal In, it is necessary to add such a reducing agent as a reduction leaching step. There is no.
【００１３】また、粗Ｉｎを得るに際して生成するソー
ダスラグの中には一般に粒状の金属Ｉｎが懸濁している
ので還元剤として適している。この金属Ｉｎが還元剤の
代用をなすばかりでなく、ソーダスラグの利用はＩｎの
回収率の面から見ても有効である。Further, since the granular metal In is generally suspended in the soda slag produced when the crude In is obtained, it is suitable as a reducing agent. Not only is this metal In used as a substitute for the reducing agent, but the use of soda slag is also effective in terms of the recovery rate of In.
【００１４】次いで、浸出液のｐＨ値を１．５〜２．５
に規定したのは、金属Ｃｄ板を用いた置換反応を有効に
作用させるためのものであり、ｐＨ値が１．５未満では
ＩｎとＣｄの酸化還元電位の差が殆ど無いのでＩｎの析
出速度が遅くなってくるためであり、逆に、ｐＨ値が
２．５を超えるとＩｎ（ＯＨ）3 の生成が加速されこと
から、Ｃｄ板表面へのＩｎの析出現象が妨げられて来る
ようになるためである。Then, the pH value of the leachate is adjusted to 1.5 to 2.5.
The reason for this is that the substitution reaction using a metal Cd plate is effectively made to work. When the pH value is less than 1.5, there is almost no difference in the redox potential between In and Cd. On the contrary, since the production of In (OH) 3 is accelerated when the pH value exceeds 2.5, the precipitation phenomenon of In on the surface of the Cd plate is hindered. This is because
【００１５】金属Ｃｄとして板を用いたのは、その表面
に析出してくるセメントＩｎをはぎ取って工程を進める
際に、剥ぎ取りを容易にすると共に、その剥ぎ取ったセ
メントＩｎの中に未反応のＣｄを介在させないためであ
り、金属Ｃｄを粉末やショットの形状で工程中に供した
のではこの目的が充分に達成出来ないからである。The plate is used as the metal Cd because it facilitates the stripping of the cement In deposited on the surface when the process proceeds and the unreacted in the stripped cement In. This is because no Cd is interposed, and if the metal Cd is provided in the form of powder or shot during the process, this object cannot be sufficiently achieved.
【００１６】剥ぎ取ったセメントＩｎに対して５〜２０
重量％のＮａＯＨを添加して融解するのは、ＮａＯＨの
添加量が５％未満では融解時にセメントＩｎが酸化され
やすくなるためであり、その量が逆に２０重量％を超え
ると処理するソーダスラグの量がいたずらに多くなって
くるためである。また、融解温度を摂氏２００〜３００
度とするのは、２００度未満の融解温度で処理したので
はスラグの流動性が悪くなってソーダスラグと粗Ｉｎと
の分離が容易でなくなるためであり、３００度を超えて
の融解処理ではＩｎの回収性に問題はないものの、高温
処理による作業効率に向上が認められないことと省エネ
ルギーの面から見て得策とは成り得ないためである。5 to 20 relative to the stripped cement In
The reason why the addition of NaOH by weight is to melt is that if the amount of NaOH added is less than 5%, the cement In tends to be oxidized during melting, and conversely if the amount exceeds 20% by weight, the soda slag to be treated is This is because the amount becomes unnecessarily large. In addition, the melting temperature is set to 200 to 300 degrees Celsius.
The reason is that if the melting temperature is less than 200 degrees, the fluidity of the slag is deteriorated and it becomes difficult to separate the soda slag and the crude In. If the melting temperature exceeds 300 degrees, Although there is no problem in recoverability, it is not a good idea from the viewpoint of energy saving and that improvement in work efficiency by high temperature treatment is not recognized.
【００１７】Ｉｎを置換析出した後の尾液に対してアル
カリ溶液を添加することにより尾液のｐＨ値を４〜６に
調整して尾液中に残存しているＩｎの回収を計っている
が、この場合、そのｐＨ値を４〜６に調整したのは、ｐ
Ｈの値が４未満ではＩｎを回収するためのＩｎ（ＯＨ）
3 が充分に生成されず、逆に、その値が６を超えるとＣ
ｄまでが水酸化物になってしまい、繰り返す水酸化物が
増加するのみでなく、尾液よりのＣｄの直接回収率を低
下させてしまうことになるからである。The pH value of the tail solution is adjusted to 4 to 6 by adding an alkaline solution to the tail solution after substitution and precipitation of In, and recovery of In remaining in the tail solution is attempted. However, in this case, the pH value was adjusted to 4 to 6 by p
In (OH) for recovering In when the H value is less than 4
If 3 is not sufficiently generated and conversely the value exceeds 6, C
This is because not only the hydroxide up to d becomes hydroxide and the number of repeated hydroxides increases, but also the direct recovery rate of Cd from the tail fluid decreases.
【００１８】以上のようにして回収した粗Ｉｎは１〜３
重量％のＣｄを含むものの、ＴｅやＡｓを殆ど含まれな
いことから高純度Ｉｎを製造するに際して、塩素錯体と
してのＣｄを形成させたのち、アニオン交換樹脂を利用
した電解精製装置を用いてＣｄを捕捉し、ここにＺｎ製
錬の中間物からその最終目的とする精製Ｉｎを容易に電
解精製して純度が９９．９９％のＩｎを容易に入手し得
た。The crude In recovered as described above is 1 to 3
Although it contains Cd in an amount of wt% but contains almost no Te or As, when producing high-purity In, Cd as a chlorine complex is formed, and then Cd is formed using an electrolytic purification apparatus using an anion exchange resin. The purified In, which is the final object, was easily electrolytically refined from the intermediate product of Zn smelting, and In having a purity of 99.99% could be easily obtained.
【００１９】なお、板状のＣｄの表面にセメントＩｎを
置換析出させるために、以下の実施例では、板状のＣｄ
の周囲に液循環を行わせているが、本発明は液循環に限
られない。すなわち、板状のＣｄを液中で揺動させた
り、液を単に攪拌させてもよい。In order to substitute and deposit the cement In on the surface of the plate-shaped Cd, the plate-shaped Cd is used in the following examples.
Although the liquid circulation is performed around, the present invention is not limited to the liquid circulation. That is, the plate-shaped Cd may be swung in the liquid, or the liquid may be simply stirred.
【００２０】[0020]
【実施例】以下、本発明の実施例について詳述する。EXAMPLES Examples of the present invention will be described in detail below.
【００２１】[0021]
【実施例１】重量％にて、水分が２４．３％であり、Ｉ
ｎが４８．４％であり、Ｃｄが４０．６％であり、Ｔｅ
が１．７％であり、Ａｓが０．０２％であり、湿量が３
３５ｋｇ（乾量が２５４ｋｇ）である含Ｉｎセメントに
対して、３５重量％のＨＣｌを５５０リットル添加した
状態で凡そ１８時間にわたって攪拌した後、２５０ｇ／
リットルの濃度に調整されているＮａＯＨを１６０リッ
トル添加してｐＨが２．０の溶液を作成し、この溶液を
濾過して黒色を呈する残渣を湿量で２４ｋｇと濾液１３
４０リットルを得た。Example 1 Moisture content is 24.3% by weight and I
n is 48.4%, Cd is 40.6%, Te
Is 1.7%, As is 0.02%, and the moisture content is 3
To In-containing cement of 35 kg (dry weight of 254 kg), 550 liters of 35 wt% HCl was added and stirred for about 18 hours, and then 250 g /
A solution having a pH of 2.0 was prepared by adding 160 liters of NaOH adjusted to a concentration of 1 liter, and the solution was filtered to give a black residue of 24 kg in a wet amount and a filtrate 13
40 liters were obtained.
【００２２】この場合、得られた残渣の組成は重量％に
て水分が３８．１％であり、Ｃｄが２０．８％であり、
Ｉｎが９．８％であり、Ｔｅが２５．４％であり、Ａｓ
が０．２８％であった。In this case, the composition of the obtained residue is 38.1% by weight of water, 20.8% of Cd, and
In is 9.8%, Te is 25.4%, As is
Was 0.28%.
【００２３】また、得られた濾液の組成はＩｎが９８．
０ｇ／リットルであり、Ｃｄが８８．７ｇ／リットルで
あり、Ｔｅが０．００５ｇ／リットル以下であり、Ａｓ
が０．０００５ｇ／リットルであって、濾液の組成とし
てはＴｅとＡｓが殆ど含まれていなかった。The composition of the obtained filtrate was 98.
0 g / liter, Cd is 88.7 g / liter, Te is 0.005 g / liter or less, As
Was 0.0005 g / liter, and the composition of the filtrate contained almost no Te and As.
【００２４】このＴｅとＡｓが殆ど含まれていない濾液
の中に総表面積が４．９ｍ2 となるように金属Ｃｄの板
材を浸漬して、この金属Ｃｄの板材の周囲を毎分４０リ
ットルの割合で７２時間にわたって上記の濾液を循環さ
せた後、Ｃｄ板の表面に析出していたセメントＩｎをＣ
ｄ板の表面から剥ぎ取り、充分に水洗し、乾燥し、さら
にＮａＯＨの１５ｋｇを合わせた混合物をステンレス製
のるつぼを用いて摂氏２５０度にて融解し、上下に分離
したソーダスラグ２８ｋｇと粗Ｉｎ１２６ｋｇとを得
た。ソーダスラグはすくい取って粗Ｉｎから分離した。A metal Cd plate was immersed in the filtrate containing almost no Te and As so as to have a total surface area of 4.9 m 2, and 40 liters / min of the metal Cd plate was surrounded. After the above filtrate was circulated for 72 hours at a ratio, the cement In deposited on the surface of the Cd plate was replaced with C
Stripped from the surface of d plate, washed thoroughly with water, dried, and melted a mixture of 15 kg of NaOH at 250 degrees Celsius using a stainless steel crucible. Got The soda slag was skimmed and separated from the crude In.
【００２５】この場合に得られたソーダスラグの組成は
重量％にて、Ｉｎが１９．３％であり、Ｃｄが０．９０
％であり、Ｔｅが０．０２２％であり、Ａｓが０．００
４％であった。The composition of the soda slag obtained in this case was 19.3% In and Cd 0.90% by weight.
%, Te is 0.022%, As is 0.00
It was 4%.
【００２６】また、粗Ｉｎの組成は重量％にて、Ｉｎが
９８．６％であり、Ｃｄが１．２２％であり、Ｔｅが
０．００１％以下であり、Ａｓが０．００１％以下であ
って、粗ＩｎにはＴｅとＡｓが殆ど認められない状態で
あった。ＴｅとＡｓが実質的にソーダスラグに分配され
ていることがわかる。The composition of crude In is, in wt%, In: 98.6%, Cd: 1.22%, Te: 0.001% or less, As: 0.001% or less. However, Te and As were hardly found in the crude In. It can be seen that Te and As are substantially distributed in the soda slag.
【００２７】なお、金属Ｃｄの板材の周囲を毎分４０リ
ットルの割合で７２時間にわたって上記の濾液を循環さ
せた後、Ｃｄ板の表面に析出していたセメントＩｎをＣ
ｄ板の表面から剥ぎ取った時点で得られた尾液の組成
は、１リットルの尾液の中にＩｎを６．３ｇと、Ｃｄを
２０８ｇと、Ｔｅを０．００５ｇ以下と、Ａｓを０．０
００５ｇ以下とを含むものであって、この尾液にＮａＯ
Ｈが２５０ｇ／リットルの割合で含まれる水溶液を３５
リットル使用してｐＨを５．５に調整し、１６時間かけ
て静置沈降させて４５０リットルのＩｎ（ＯＨ）3 相と
１０４０リットルのＣｄＳＯ4 相を得た。After circulating the above filtrate around the metal Cd plate at a rate of 40 liters per minute for 72 hours, the cement In deposited on the surface of the Cd plate was replaced with C.
The composition of the tail solution obtained when it was peeled off from the surface of the d plate was as follows: 1 liter of tail solution contained 6.3 g of In, Cd of 208 g, Te of 0.005 g or less, and As of 0. .0
005 g or less, and the tail solution contains NaO
An aqueous solution containing H at a rate of 250 g / liter is used.
The pH was adjusted to 5.5 using liters and allowed to settle for 16 hours to give 450 liters of In (OH) 3 phase and 1040 liters of CdSO 4 phase.
【００２８】この場合、Ｉｎ（ＯＨ）3 相の組成は１リ
ットル当たりＩｎが２０．６ｇであり、ＣｄＳＯ4 相の
組成は１リットル当たり、Ｃｄが１９５ｇであり、Ｉｎ
が０．００４ｇであり、Ｔｅが０．００５ｇ以下であ
り、Ａｓが０．０００５ｇ以下であった。ＣｄＳＯ4 相
の不純物が極めて少なく、Ｃｄ回収に有利であることが
わかる。In this case, the composition of the In (OH) 3 phase was 20.6 g of In per liter, and the composition of the CdSO 4 phase was 195 g of Cd per liter.
Was 0.004 g, Te was 0.005 g or less, and As was 0.0005 g or less. It can be seen that impurities in the CdSO 4 phase are extremely small, which is advantageous for Cd recovery.
【００２９】なお、ＡｓＨ3 ガスの発生を検知器で調べ
たが浸出時及び置換析出時とも検出されなかった。The generation of AsH 3 gas was examined by a detector, but it was not detected during leaching or substitution precipitation.
【００３０】[0030]
【実施例２】１リットル中にＣｄを８３．９ｇと、Ｉｎ
を１０．６ｇと、Ｔｅを０．４２ｇと、Ａｓを０．０１
８ｇと、遊離Ｈ2 ＳＯ4 を１１０ｇの割合で含んだ含Ｉ
ｎ水溶液を１０７０リットル用意すると共に、組成が重
量％にて、Ｉｎが１９．３％であり、Ｃｄが０．９０％
であり、Ｔｅが０．０２２％であり、Ａｓが０．００４
％であるソーダスラグを２８ｋｇと、実施例１で得たＩ
ｎ（ＯＨ）3 相を４５０リットルと、粉末状で湿量５ｋ
ｇ（乾量４．６ｋｇ）のＣｄ品位が９８．４重量％であ
る還元剤としてのセメントＣｄとを約１時間にわたって
撹拌し、混合した後、さらに、１リットル中に２５０ｇ
の割合でＮａＯＨが含まれる苛性ソーダ水溶液を２９０
リットル加えｐＨを２．０の水溶液とし、この水溶液を
濾過して湿量９．４ｋｇの残渣と１８４０リットルの濾
液とを得た。Example 2 83.9 g of Cd in 1 liter and In
10.6g, Te 0.42g, As 0.01
Containing 8 g and free H 2 SO 4 at a ratio of 110 g
1070 liters of an aqueous solution of n are prepared, the composition is wt%, In is 19.3%, and Cd is 0.90%.
And Te is 0.022% and As is 0.004.
% Soda slag of 28 kg and I obtained in Example 1
450 liters of n (OH) 3 phase, powdery and wet 5k
g (dry weight 4.6 kg), Cd as a reducing agent and cement Cd having a quality of 98.4 wt% were stirred for about 1 hour and mixed, and then 250 g was added to 1 liter.
290 with a caustic soda solution containing NaOH at a ratio of
L was added to make an aqueous solution having a pH of 2.0, and this aqueous solution was filtered to obtain a residue having a wet weight of 9.4 kg and a filtrate having 1840 liters.
【００３１】この場合、得られた残渣の組成は重量％に
て、水分が３６．１％であり、Ｃｄが２４．６％であ
り、Ｉｎが７．８％であり、Ｔｅが７．６％であり、Ａ
ｓが０．３１％であると共に、濾液の組成は１リットル
当たりＣｄが９３．９ｇであり、Ｉｎが１４．６ｇであ
り，Ｔｅが０．００５ｇ以下であり、Ａｓが０．０００
７ｇであった。In this case, the composition of the obtained residue is 36.1% by weight, water is 36.1%, Cd is 24.6%, In is 7.8%, and Te is 7.6. %, And A
s is 0.31%, and the composition of the filtrate is such that Cd is 93.9 g per liter, In is 14.6 g, Te is 0.005 g or less, and As is 0.000.
It was 7 g.
【００３２】上記の濾液に総表面積が４．９ｍ2 となる
ようにＣｄ板を浸漬し、毎分４０リットルの循環量にて
４８時間にわたって上記のＣｄ板の周囲を循環させてそ
の表面にセメントＩｎを析出させたのち、このセメント
ＩｎをＣｄ板から剥ぎ取り、次いで充分に水洗したセメ
ントＩｎに対して、さらに、ＮａＯＨの３ｋｇを添加
し、ステンレスのるつぼの中で摂氏２５０度で融解し、
上下に分離したソーダスラグの６．９ｋｇと粗Ｉｎの２
３．２ｋｇとを得た。A Cd plate was dipped in the above filtrate so that the total surface area was 4.9 m 2, and was circulated around the Cd plate for 48 hours at a circulation rate of 40 liters per minute to cement the surface thereof. After precipitation of In, the cement In was peeled off from the Cd plate, and then 3 kg of NaOH was further added to the cement In that had been sufficiently washed with water, and melted at 250 degrees Celsius in a stainless crucible,
6.9 kg of soda slag separated from the top and bottom and 2 of crude In
I got 3.2 kg.
【００３３】この場合に得られたソーダスラグの組成は
重量％にて、Ｉｎが１７．４％であり、Ｃｄが１．１％
であり、Ｔｅが０．０６１％であり、Ａｓが０．０１０
％であった。The composition of the soda slag obtained in this case was 17.4% In and Cd 1.1% by weight.
And Te is 0.061% and As is 0.010.
%Met.
【００３４】一方、粗Ｉｎの組成は、重量％で、Ｉｎが
９８．０４％であり、Ｃｄが１．７６％であり、Ｔｅが
０．００１５以下であり、Ａｓが０．００１％以下であ
った。Ｔｅ、Ａｓがほとんどソーダスラグに分配された
ことがわかる。On the other hand, the composition of crude In is as follows: wt%, In is 98.04%, Cd is 1.76%, Te is 0.0015 or less, As is 0.001% or less. there were. It can be seen that Te and As were mostly distributed in the soda slag.
【００３５】また、置換析出後の尾液は、１リットル当
たり、Ｃｄ１１６ｇ、Ｉｎ０．９７ｇ、Ｔｅ０．００５
ｇ以下、Ａｓ０．０００５ｇ以下を含有し、１リットル
当たり２５０ｇのＮａＯＨ水溶液を５５リットル使用し
てｐＨ５．０に調整し、１６時間静置沈降させてＩｎ
（ＯＨ）3 相１００リットルとＣｄＳＯ4 相１８３０リ
ットルを得た。Ｉｎ（ＯＨ）3 相の品位は、１リットル
当たりＩｎ１９．６ｇでＩｎが濃縮され、ＣｄＳＯ4 相
の品位は、１リットル当たりＣｄ１１１ｇ、Ｉｎ０．０
０９ｇ、Ｔｅ０．００５ｇ以下、Ａｓ０．０００５ｇ以
下であり、不純物の少ないＣｄＳＯ4 水溶液を得た。Further, the tail solution after the substitution precipitation is 116 g of Cd, 0.97 g of In, and 0.005 Te per liter.
g or less, As 0.0005 g or less, and adjusted to pH 5.0 using 55 liters of 250 g of NaOH aqueous solution per liter, and allowed to stand for 16 hours for sedimentation.
100 liters of (OH) 3 phase and 1830 liters of CdSO 4 phase were obtained. The In (OH) 3 phase had a concentration of In of 19.6 g per liter and was enriched with In, and the CdSO 4 phase had a grade of Cd of 111 g per liter and In0.0.
A CdSO 4 aqueous solution containing 09 g, Te of 0.005 g or less and As of 0.0005 g or less and containing few impurities was obtained.
【００３６】なお、ＡｓＨ3 ガスの発生は、検知器で調
べたが、浸出時及び置換析出時とも検出されなかった。Generation of AsH 3 gas was examined by a detector, but it was not detected at the time of leaching and at the time of substitution and precipitation.
【００３７】[0037]
【従来例】実施例２と同様に調整された含Ｉｎ水溶液１
０２０リットルに対して、ＮａＯＨを２５０ｇ／リット
ルの濃度割合で含むアルカリ水溶液の２１０リットルを
添加してｐＨが２．０の含Ｉｎ水溶液を用意し、この含
Ｉｎ水溶液を濾過したところ、発生残渣は０．２ｋｇと
少なく、１２４０リットルの濾液を得た。PRIOR ART In-containing aqueous solution 1 prepared in the same manner as in Example 2
When 210 liters of an alkaline aqueous solution containing NaOH at a concentration ratio of 250 g / liter was added to 020 liters to prepare an In-containing aqueous solution having a pH of 2.0, and the In-containing aqueous solution was filtered. As little as 0.2 kg, 1240 liters of filtrate was obtained.
【００３８】この場合、濾液の組成は、１リットル当た
り、Ｃｄを６９．０ｇと，Ｉｎを８．７ｇと、Ｔｅを
０．３４ｇと、Ａｓを０．０１５ｇ含有していた。In this case, the composition of the filtrate contained 69.0 g of Cd, 8.7 g of In, 0.34 g of Te, and 0.015 g of As per liter.
【００３９】上記の組成を持った濾液に対して、金属Ｚ
ｎ粉末を９．２ｋｇ添加して緩やかに撹拌し、ＡｓＨ3
の発生状況を調査したところ、その検出量はピーク時に
２．８ｐｐｍを示した。For the filtrate having the above composition, metal Z
n powder was added in 9.2 kg and gently stirred to remove AsH 3
As a result of investigating the occurrence situation of the, the detected amount was 2.8 ppm at the peak.
【００４０】１６時間の撹拌作業の後に得たセメントＩ
ｎは実施例２の場合に比較して泥状であると共に、その
水溶液も黒色を示していた。Cement I obtained after 16 hours of stirring
n was muddy as compared with the case of Example 2, and the aqueous solution thereof was also black.
【００４１】この様にして泥状のセメントＩｎを得た後
の尾液の組成は、１リットル中にＣｄを６８．１ｇと、
Ｉｎを１．３２ｇと、Ｔｅを０．０２ｇ以下と、Ａｓを
０．００１ｇとを含んでいた。The composition of the tail fluid after the mud-like cement In was thus obtained was 68.1 g of Cd in 1 liter,
It contained 1.32 g of In, 0.02 g or less of Te, and 0.001 g of As.
【００４２】また、ここで得た泥状のセメントＩｎにＮ
ａＯＨを１．２ｋｇ添加し、ステンレス製のるつぼを用
いて摂氏２５０度で融解したところ、セメントＩｎの一
部が燃焼現象を示したため、直ちにＮａＯＨを１．０ｋ
ｇ添加した。In addition, N was added to the mud-like cement In obtained here.
When 1.2 kg of aOH was added and melted at 250 degrees Celsius using a stainless crucible, a part of the cement In showed a combustion phenomenon, and NaOH 1.0 k was immediately added.
g was added.
【００４３】この様にして得られたソーダスラグの重量
は６．７ｋｇであり、粗Ｉｎの重量は８．１ｋｇであっ
た。The soda slag thus obtained weighed 6.7 kg and the crude In weighed 8.1 kg.
【００４４】また、この場合のソーダスラグの組成は重
量％でＩｎが１９．８％であり、Ｃｄが５．８％であ
り、Ｔｅが５．１％であり、Ａｓが０．０９％であり、
同じく粗Ｉｎの組成は、Ｉｎが９４．８％であり、Ｃｄ
が４．１３％であり、Ｔｅが０．００１％以下であり、
Ａｓが０．００１％以下であった。The composition of the soda slag in this case was 19.8% by weight, Cd was 5.8%, Te was 5.1% and As was 0.09%. ,
Similarly, the composition of crude In is 94.8% In,
Is 4.13%, Te is 0.001% or less,
As was 0.001% or less.
【００４５】以上のように、本発明によるときは、Ｉｎ
の含有度の高い製品を安易な方法で製造できるようにす
ると共に、硫化作業にて精製除去せざるを得ないＴｅや
Ａｓなどの有害物質の巻き込みを殆ど防止することの可
能性を開示し得た。As described above, according to the present invention, In
It may be possible to disclose the possibility of making it possible to manufacture a product with a high content of a simple method and to prevent the inclusion of harmful substances such as Te and As, which must be purified and removed by a sulfiding operation. It was
【００４６】[0046]
【発明の効果】以上に述べたように、本発明によれば、
極めて簡便な手段にてＴｅやＡｓ等の含有量の極めて少
ない粗Ｉｎの回収を可能にし、これが、高純度Ｉｎを製
造する際の環境汚染物質である硫化物の生成を極めて極
小にする方法を開示出来たので斯る手段によって市場に
Ｉｎ製品を送り出している産業界に寄与するところ大な
るものがある。As described above, according to the present invention,
With a very simple means, it is possible to recover crude In having a very small content of Te, As, etc., which minimizes the production of sulfide, which is an environmental pollutant when producing high-purity In. Since it was possible to disclose it, there is a great contribution to the industry sending In products to the market by such means.
【図１】本発明の方法の実施例に係るフローチャートで
ある。1 is a flow chart according to an embodiment of the method of the present invention.
Claims (2)
ｄ、Ｚｎ、Ｉｎ、Ｔｅ、Ａｓ等を含有した中間物よりＩ
ｎを回収するに際して、還元剤としてＴｅ化合物やＡｓ
化合物を生成させるに必要な量の２当量以上の金属Ｃｄ
と金属Ｉｎもしくはこのような量の金属ＣｄとＩｎを含
有する還元用澱物を用いて上記中間物を鉱酸酸性下で還
元浸出して浸出液とし、この浸出液に水酸化アルカリ水
溶液を添加してｐＨを１．５〜２．５に調整し、この液
から残渣を分離して得た濾液中に板状のＣｄを浸漬し、
板状のＣｄの表面にセメントＩｎを置換析出させ、板状
のＣｄの表面より剥離して得たセメントＩｎに、該セメ
ントＩｎに対して５〜２０重量％のＮａＯＨを添加して
後、摂氏２００〜３００度で融解して、発生したソーダ
スラグを層分離して粗Ｉｎを回収することを特徴とする
Ｉｎの回収方法。1. C generated in a Zn smelting process
I from the intermediate containing d, Zn, In, Te, As, etc.
When recovering n, Te compound or As
2 equivalents or more of the metal Cd necessary for forming the compound
And the metal In or the reducing starch containing such amounts of the metal Cd and In, the intermediate is subjected to reduction leaching under acidic acid of mineral acid to obtain a leachate, and an alkali hydroxide aqueous solution is added to the leachate. The pH was adjusted to 1.5 to 2.5, plate-like Cd was immersed in the filtrate obtained by separating the residue from this solution,
Cement In was substituted and precipitated on the surface of the plate-shaped Cd, and 5 to 20% by weight of NaOH was added to the cement In obtained by peeling from the surface of the plate-shaped Cd. A method for recovering In, comprising melting at 200 to 300 ° C., separating the generated soda slag into layers, and recovering crude In.
に、アルカリ水溶液を添加して、そのｐＨを４〜６に調
整し、生成した沈澱物を中間物の鉱酸酸性下における還
元浸出時に添加することを特徴とする請求項１に記載の
Ｉｎの回収方法。2. An alkaline aqueous solution is added to the tail solution after substitution and precipitation of cement In to adjust its pH to 4 to 6, and the resulting precipitate is subjected to reduction leaching of the intermediate under acidity of mineral acid. The method for recovering In according to claim 1, wherein the method is added at the same time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29913492A JP3024396B2 (en) | 1992-10-13 | 1992-10-13 | In recovery method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29913492A JP3024396B2 (en) | 1992-10-13 | 1992-10-13 | In recovery method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06128664A true JPH06128664A (en) | 1994-05-10 |
| JP3024396B2 JP3024396B2 (en) | 2000-03-21 |
Family
ID=17868568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29913492A Expired - Lifetime JP3024396B2 (en) | 1992-10-13 | 1992-10-13 | In recovery method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3024396B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006241479A (en) * | 2005-02-28 | 2006-09-14 | Mitsui Mining & Smelting Co Ltd | Method for producing indium-containing metal |
| JP2007270342A (en) * | 2006-03-06 | 2007-10-18 | Kobelco Eco-Solutions Co Ltd | Process for recovery of indium and equipment therefor |
| WO2008090671A1 (en) * | 2007-01-23 | 2008-07-31 | Sharp Kabushiki Kaisha | Method and apparatus for collection of indium from etching waste solution containing indium and ferric chloride |
| WO2008090672A1 (en) * | 2007-01-23 | 2008-07-31 | Sharp Kabushiki Kaisha | Method and apparatus for collection of indium from etching waste solution containing indium and ferric chloride |
-
1992
- 1992-10-13 JP JP29913492A patent/JP3024396B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006241479A (en) * | 2005-02-28 | 2006-09-14 | Mitsui Mining & Smelting Co Ltd | Method for producing indium-containing metal |
| JP2007270342A (en) * | 2006-03-06 | 2007-10-18 | Kobelco Eco-Solutions Co Ltd | Process for recovery of indium and equipment therefor |
| WO2008090671A1 (en) * | 2007-01-23 | 2008-07-31 | Sharp Kabushiki Kaisha | Method and apparatus for collection of indium from etching waste solution containing indium and ferric chloride |
| WO2008090672A1 (en) * | 2007-01-23 | 2008-07-31 | Sharp Kabushiki Kaisha | Method and apparatus for collection of indium from etching waste solution containing indium and ferric chloride |
| JP5068772B2 (en) * | 2007-01-23 | 2012-11-07 | シャープ株式会社 | Method for recovering indium from an etching waste solution containing indium and ferric chloride |
| JP5068773B2 (en) * | 2007-01-23 | 2012-11-07 | シャープ株式会社 | Method for recovering indium from an etching waste solution containing indium and ferric chloride |
| US8480785B2 (en) | 2007-01-23 | 2013-07-09 | Sharp Kabushiki Kaisha | Method and apparatus for recovering indium from etching waste solution containing indium and ferric chloride |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3024396B2 (en) | 2000-03-21 |
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