JP2007009274A - Method for recovering indium - Google Patents

Method for recovering indium Download PDF

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JP2007009274A
JP2007009274A JP2005191055A JP2005191055A JP2007009274A JP 2007009274 A JP2007009274 A JP 2007009274A JP 2005191055 A JP2005191055 A JP 2005191055A JP 2005191055 A JP2005191055 A JP 2005191055A JP 2007009274 A JP2007009274 A JP 2007009274A
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tin
indium
precipitate
acid
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Masaharu Ishiwatari
正治 石渡
Fumio Watanabe
文雄 渡辺
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Mitsubishi Materials Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method where separability of indium and tin is excellent, and, even from an indium-tin alloy having a high tin content, indium having a remarkably low tin content can be recovered. <P>SOLUTION: In the method for recovering indium, an indium-tin-containing material (such as an In-Sn alloy) containing indium and tin in metal form is dissolved into a hydrochloric acid, sulfuric acid or a mixed acid of hydrochloric acid and sulfuric acid, oxalic acid is added to the solution so as to precipitate tin oxalate, preferably, under the liquefaction of pH 0.5 to 3, then, the tin oxalate precipitates are subjected to solid-liquid separation, indium metal is added to the tin oxalate filtrate, the remaining tin is precipitated so as to remove tin, and base metals such as zinc, aluminum and iron are added to the tin-removed filtrate so as to precipitate indium, thus spongy metal indium is recovered. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、インジウム−スズ含有物からインジウムを効率よくスズと分離して回収する方法に関し、より詳しくは、スズ含有量が多いインジウム−スズ合金からインジウムをスズと分離して効率よく回収することができるインジウムの回収方法に関する。 The present invention relates to a method for efficiently separating and recovering indium from indium-tin-containing materials, and more particularly to efficiently recovering indium by separating it from tin from an indium-tin alloy having a high tin content. The present invention relates to a method for recovering indium.

インジウムの回収技術として、インジウムスズ含有物を硫酸で溶解して回収する方法が知られている（特許文献１）。しかし、この回収方法は硫酸溶液中のインジウム濃度が低く、またスズの混入が避けられず、回収費用が嵩む問題点があった。さらに、分離工程で使用する水酸化ナトリウムと硫酸が反応して硫酸ナトリウムが生成するため、低温時には液中に結晶が析出してトラブルが起こり易い難点があった。 As a technique for recovering indium, a method is known in which an indium tin-containing material is recovered by dissolving with sulfuric acid (Patent Document 1). However, this recovery method has a problem that the concentration of indium in the sulfuric acid solution is low, and tin is unavoidably mixed, which increases the recovery cost. Furthermore, since sodium hydroxide used in the separation step reacts with sulfuric acid to produce sodium sulfate, there is a problem that crystals are likely to precipitate in the liquid at low temperatures and troubles are likely to occur.

上記硫酸溶解法に代えて、硝酸を用いる方法が知られている。この方法は、ＩＴＯスクラップ等を硝酸に混合して、酸化インジウムを溶解させる一方、硝酸に不溶性の酸化スズを溶解残として分離する方法であり、スズを分離した後は、インジウム硝酸溶解液を陽イオン交換型の抽出溶媒に接触させてインジウムを抽出する方法（特許文献２）や、インジウム硝酸溶解液に硫化水素を通して、亜鉛、スズ 、鉛、銅などの不純物を硫化物として沈殿除去した後、これにアンモニアを加えて中和し、水酸化インジウムとして回収する方法が知られている。 Instead of the sulfuric acid dissolution method, a method using nitric acid is known. In this method, ITO scrap or the like is mixed with nitric acid to dissolve indium oxide, while insoluble nitric oxide in nitric acid is separated as a dissolution residue. After the tin is separated, the indium nitric acid solution is positively mixed. After extracting indium by bringing it into contact with an ion-exchange type extraction solvent (Patent Document 2) or passing hydrogen sulfide through an indium nitrate solution to precipitate impurities such as zinc, tin, lead and copper as sulfides, A method is known in which ammonia is added thereto to neutralize and recovered as indium hydroxide.

しかし、有機抽出溶媒を用いてインジウムを抽出する方法はコストが嵩み、またインジウム硝酸溶解液に共存する他の金属イオンの存在によって抽出効果が影響を受けるなどの問題がある。また、インジウム硝酸溶解液から亜鉛、スズ 、鉛、銅などの不純物を硫化物沈澱にして分離除去した後に、インジウムを水酸化沈澱にして回収する従来の方法は、この水酸化インジウムの濾過性が悪いために分離操作に長時間を要し、しかも中和条件および熟成条件等によって粒径や粒度分布がかなり変動するため、これをＩＴＯターゲット材料として使用すると、ＩＴＯターゲットの特性を安定して維持できないという問題がある。 However, the method of extracting indium using an organic extraction solvent has a problem that the cost is high and the extraction effect is affected by the presence of other metal ions that coexist in the indium nitrate solution. In addition, the conventional method in which impurities such as zinc, tin, lead, and copper are separated and removed from a solution of indium nitric acid by sulfide precipitation, and then recovered by precipitation of indium by hydroxide precipitation. Because it is bad, the separation operation takes a long time, and the particle size and particle size distribution vary considerably depending on the neutralization and aging conditions. When used as an ITO target material, the characteristics of the ITO target can be maintained stably. There is a problem that you can not.

一方、ＩＴＯスクラップを塩酸に溶解させ、水酸化ナトリウムを添加して水酸化スズの沈澱を生成させ、これを濾過してインジウムと分離する方法も知られている（特許文献３、４）。しかし、この方法ではスズが完全に沈澱化せずに残留し、また水酸化スズの濾過性が悪いので、スズ混入量の少ないインジウムを回収するのが難しいと云う問題がある。 On the other hand, a method is also known in which ITO scrap is dissolved in hydrochloric acid, sodium hydroxide is added to form a precipitate of tin hydroxide, and this is filtered and separated from indium (Patent Documents 3 and 4). However, this method has a problem that it is difficult to recover indium with a small amount of tin contamination because tin remains without being completely precipitated and the filterability of tin hydroxide is poor.

また、ＩＴＯスクラップの塩酸溶解液や硝酸溶解液にシュウ酸化合物を添加してシュウ酸インジウム沈澱を生成させ、これから酸化インジウムを回収する方法が知られている（特許文献５）。しかし、この方法は、ＩＴＯスクラップを硝酸に溶解することによってスズを不溶性のメタスズ酸として予め分離するか、或いは、ＩＴＯスクラップを塩酸に溶解した後にハロゲノスズ酸塩として予め分離する必要があり、スズをシュウ酸塩として沈澱分離する方法ではなく、スズの分離性が低く、また、スズ分離後のインジウム回収工程が煩雑であるためコスト高になる問題がある。
特開昭５５−４１９９８号公報 特開２０００−１２８５３１号公報 特開２００２−６９５４４号公報 特開２００２−２０１０２５号公報 特開平０３−１９９１２２号公報 Further, a method is known in which an oxalic acid compound is added to a hydrochloric acid solution or a nitric acid solution of ITO scrap to generate an indium oxalate precipitate, and indium oxide is recovered therefrom (Patent Document 5). However, this method requires either pre-separation of tin as insoluble metastannic acid by dissolving ITO scrap in nitric acid, or pre-separation as halogenostannate after dissolving ITO scrap in hydrochloric acid. This is not a method for precipitation separation as an oxalate, but has a problem that the separability of tin is low and the indium recovery step after the separation of tin is complicated, resulting in high costs.
JP 55-41998 A JP 2000-128531 A JP 2002-69544 A JP 2002-201025 A Japanese Patent Laid-Open No. 03-199122

本発明は、従来の方法における上記問題を解決したものであり、インジウムとスズの分離性が良く、スズ混入量の極めて少ないインジウムを回収することができる方法を提供する。 The present invention solves the above-mentioned problems in the conventional method, and provides a method capable of recovering indium with a good separation of indium and tin and a very small amount of tin.

本発明によれば以下のインジウム回収方法とその用途が提供される。
（１）インジウムとスズを金属形態で含有するインジウム−スズ含有物を塩酸、硫酸、または塩酸と硫酸の混酸に溶解し、この溶解液にシュウ酸化合物を添加してシュウ酸スズ沈澱を生成させ、このシュウ酸スズ沈澱を固液分離した濾液にインジウムまたは亜鉛またはアルミニウムを添加して濾液に残留するスズを析出させて固液分離し、この脱スズ濾液に卑金属を添加してインジウムを析出させ、スポンジ状の金属インジウムを回収することを特徴とするインジウムの回収方法。
（２）上記(1)の方法において、Ｉｎ−Ｓｎ合金を出発原料として用いるインジウムの回収方法。
（３）Ｉｎ−Ｓｎ合金を、塩酸または硫酸または塩酸と硫酸の混酸に溶解し、この溶解液にシュウ酸化合物とアルカリ化合物とを添加し、ｐＨ０.５〜３の液性下でシュウ酸スズ沈澱を生成させ、シュウ酸スズ沈澱を固液分離した濾液にｐＨ０.５〜２の液性下でインジウムまたは亜鉛またはアルミニウムを添加して濾液に残留するスズを析出させて固液分離し、この脱スズ濾液に亜鉛またはアルミニウムまたは鉄の少なくとも一種を添加してインジウムを析出させ、スズ含有量５ppm未満の金属インジウムを回収することを特徴とする方法。
（４）シュウ酸化合物としてシュウ酸、シュウ酸アンモニウム、アルカリ金属シュウ酸塩の少なくとも一種を用いる上記(1)〜(3)の何れかに記載するインジウムの回収方法。 According to the present invention, the following indium recovery method and its use are provided.
(1) An indium-tin-containing material containing indium and tin in a metal form is dissolved in hydrochloric acid, sulfuric acid, or a mixed acid of hydrochloric acid and sulfuric acid, and an oxalic acid compound is added to the solution to form a tin oxalate precipitate. Then, indium, zinc or aluminum is added to the filtrate obtained by solid-liquid separation of the tin oxalate precipitate to precipitate tin remaining in the filtrate and solid-liquid separation is performed, and base metal is added to the detinized filtrate to precipitate indium. A method for recovering indium, characterized by recovering sponge-like metal indium.
(2) A method for recovering indium using the In—Sn alloy as a starting material in the method (1).
(3) An In—Sn alloy is dissolved in hydrochloric acid or sulfuric acid or a mixed acid of hydrochloric acid and sulfuric acid, and an oxalic acid compound and an alkali compound are added to the dissolved solution, and tin oxalate is added under a pH of 0.5 to 3 Indium, zinc or aluminum was added to the filtrate obtained by solid-liquid separation of the tin oxalate precipitate to precipitate tin remaining in the filtrate and separated into solid and liquid. A method characterized in that at least one of zinc, aluminum, or iron is added to a tin-free filtrate to deposit indium, and metallic indium having a tin content of less than 5 ppm is recovered.
(4) The indium recovery method according to any one of the above (1) to (3), wherein at least one of oxalic acid, ammonium oxalate, and alkali metal oxalate is used as the oxalic acid compound.

本発明の回収方法は、インジウム−スズ含有物を塩酸、硫酸、または塩酸と硫酸の混酸に溶解し、この溶解液にシュウ酸化合物を添加して生成したシュウ酸スズ沈澱を固液分離する方法であり、このシュウ酸スズ沈澱の濾過性が良いので、塩酸溶解液または硫酸溶解液にシュウ酸スズ沈澱が残留せず、インジウムとスズの分離性が良く、スズ混入量が格段に少ないインジウムを回収することができる。 The recovery method of the present invention is a method for solid-liquid separation of a tin oxalate precipitate produced by dissolving an indium-tin-containing material in hydrochloric acid, sulfuric acid, or a mixed acid of hydrochloric acid and sulfuric acid, and adding an oxalic acid compound to the solution. Since the tin oxalate precipitate has good filterability, the tin oxalate precipitate does not remain in the hydrochloric acid solution or sulfuric acid solution, and the indium and tin are well separated. It can be recovered.

さらに、シュウ酸スズ沈澱を固液分離した濾液にインジウムまたは亜鉛またはアルミニウムを添加して残留するスズを析出させて固液分離することによってさらに脱スズを進めるのでスズ含有量が大幅に少ない金属インジウムを得ることができる。また、卑金属を添加してインジウムを析出させ、スポンジ状の金属インジウムを回収するので、スズ分離後の回収工程が簡単であり、低コストでインジウムを回収することができる。 Furthermore, indium, zinc, or aluminum is added to the filtrate obtained by solid-liquid separation of the tin oxalate precipitate, and the remaining tin is precipitated and further solid-liquid separated to further promote tin removal. Can be obtained. In addition, since base metal is added to deposit indium to recover sponge-like metal indium, the recovery process after separation of tin is simple, and indium can be recovered at a low cost.

本発明のインジウム回収方法は、スズとの分離性に優れているので、スズ含有量が多いインジウム−スズ合金からインジウムを回収するのに適している。従来の硝酸溶解法や塩酸溶解法は、主にＩＴＯスクラップなどを回収原料としており、一般にこのＩＴＯスクラップはインジウム量が９０wt％以上であり、インジウムを主体とするものであるので、インジウム量が少なくスズ含有量の多いスクラップを従来の回収方法によって処理しても、スズ混入量の少ない金属インジウムを回収するのは難しい。一方、本発明の回収方法によれば、スズ含有量が多いインジウム−スズ合金からでも、スズの含有量が格段に少ない金属インジウムを回収することができる。 Since the indium recovery method of the present invention is excellent in separability from tin, it is suitable for recovering indium from an indium-tin alloy having a high tin content. The conventional nitric acid dissolution method and hydrochloric acid dissolution method mainly use ITO scrap as a recovery material. Generally, this ITO scrap has an indium content of 90 wt% or more and mainly contains indium. Even if scrap having a high tin content is processed by a conventional recovery method, it is difficult to recover metal indium with a low tin content. On the other hand, according to the recovery method of the present invention, metallic indium with a remarkably low tin content can be recovered even from an indium-tin alloy having a high tin content.

本発明のインジウム回収方法を図１に示す。図示するように、本発明のインジウム回収方法は、インジウムとスズを金属形態で含有するインジウム−スズ含有物を塩酸、硫酸、または塩酸と硫酸の混酸に溶解し〔溶解工程〕、この溶解液にシュウ酸化合物を添加してシュウ酸スズ沈澱を生成させ、このシュウ酸スズ沈澱を固液分離し〔第一脱スズ工程〕、さらに、この濾液にインジウムまたは亜鉛またはアルミニウムを添加して濾液に残留するスズを析出させて固液分離し〔第二脱スズ工程〕、この脱スズ濾液に卑金属を添加してインジウムを析出させ〔インジウム析出工程〕、スポンジ状の金属インジウムを回収することを特徴とするインジウムの回収方法である。 The indium recovery method of the present invention is shown in FIG. As shown in the figure, the indium recovery method of the present invention dissolves an indium-tin-containing material containing indium and tin in a metal form in hydrochloric acid, sulfuric acid, or a mixed acid of hydrochloric acid and sulfuric acid (dissolution step), An oxalic acid compound is added to form a tin oxalate precipitate. This tin oxalate precipitate is separated into solid and liquid (first tin removal step), and indium, zinc or aluminum is further added to the filtrate to remain in the filtrate. It is characterized by precipitating tin and solid-liquid separation (second tin removal step), adding a base metal to the tin removal filtrate to precipitate indium (indium precipitation step), and collecting sponge-like metal indium. This is a method for recovering indium.

本発明の方法は、インジウムとスズを金属形態で含有するインジウム−スズ含有物を原料とする。インジウムとスズを金属形態で含有するインジウム−スズ含有物とは、例えばＩｎ−Ｓｎ合金、あるいはＩｎ−Ｓｎスポンジである。本発明の回収方法では、インジウム含有量がスズ含有量よりも少ないＩｎ−Ｓｎ含有物、例えば、インジウム含有量が３０wt％以下のＩｎ−Ｓｎ合金、あるいはインジウム含有量が３０wt％以下のＩｎ−Ｓｎスポンジを原料として用いることができ、スズ含有量の少ない金属インジウムを回収することができる。 The method of the present invention uses an indium-tin-containing material containing indium and tin in a metal form as a raw material. The indium-tin-containing material containing indium and tin in a metal form is, for example, an In—Sn alloy or an In—Sn sponge. In the recovery method of the present invention, an In—Sn content in which the indium content is smaller than the tin content, for example, an In—Sn alloy with an indium content of 30 wt% or less, or an In—Sn with an indium content of 30 wt% or less. Sponge can be used as a raw material, and metal indium with a small tin content can be recovered.

〔溶解工程〕
上記インジウム−スズ含有物を塩酸、硫酸、または塩酸と硫酸の混酸に溶解させる。硝酸を用いると、金属スズが硝酸と反応して不溶性のメタスズ酸沈澱を生じ、このメタスズ酸沈澱は濾過性が良くないので好ましくない。塩酸または硫酸の濃度は溶解に必要とされる酸濃度の２倍当量以上が適当であり、液温は５０℃以上、好ましくは７０℃以上が良い。 [Dissolution process]
The indium-tin-containing material is dissolved in hydrochloric acid, sulfuric acid, or a mixed acid of hydrochloric acid and sulfuric acid. When nitric acid is used, metallic tin reacts with nitric acid to produce an insoluble metastannic acid precipitate, which is not preferred because the filterability is not good. The concentration of hydrochloric acid or sulfuric acid is suitably at least 2 equivalents of the acid concentration required for dissolution, and the liquid temperature is 50 ° C or higher, preferably 70 ° C or higher.

〔第一脱スズ工程〕
上記酸溶解液にシュウ酸化合物を添加してシュウ酸スズ沈澱を生成させる。シュウ酸化合物としてはシュウ酸、シュウ酸アンモニウム、アルカリ金属シュウ酸塩などを用いることができる。この添加量は液中のスズを十分に沈澱化する量が好ましい。具体的には、液中のスズイオンに対して当量またはやや過剰量が適当である。 [First tin removal process]
An oxalic acid compound is added to the acid solution to produce a tin oxalate precipitate. As the oxalic acid compound, oxalic acid, ammonium oxalate, alkali metal oxalate and the like can be used. The amount added is preferably an amount that sufficiently precipitates tin in the liquid. Specifically, an equivalent amount or a slight excess amount is appropriate with respect to tin ions in the liquid.

シュウ酸スズを沈澱させる際に、シュウ酸化合物と共にアルカリ化合物を添加し、ｐＨ０.５〜３の液性下でシュウ酸スズ沈澱を生成させるのが好ましい。ｐＨが４を超えると水酸化インジウムの沈殿が生成するので好ましくない。またｐＨが０.５未満であるとスズの沈殿生成率が低下する。 When precipitating tin oxalate, it is preferable to add an alkali compound together with the oxalic acid compound to produce a tin oxalate precipitate under liquidity at pH 0.5-3. When the pH exceeds 4, indium hydroxide precipitates, which is not preferable. Further, when the pH is less than 0.5, the precipitation rate of tin is lowered.

生成したシュウ酸スズ沈澱を濾過し、インジウム溶解液と分離する。分離したシュウ酸スズ沈澱はスズ回収工程に送り、スズ回収原料として使用することができる。 The formed tin oxalate precipitate is filtered and separated from the indium solution. The separated tin oxalate precipitate can be sent to a tin recovery process and used as a tin recovery raw material.

〔第二脱スズ工程〕
シュウ酸スズ沈澱を分離した濾液のｐＨを０.５〜２に維持しつつ、インジウムあるいは亜鉛あるいはアルミニウムを添加し、濾液中に微量に残留するスズを還元して析出させ、このスズスポンジを固液分離して脱スズを進める。スズスポンジを除去した脱スズ液にインジウムより卑な金属を添加してインジウムを還元析出させることによって、スズ含有量が格段に少ないスポンジ状の金属インジウムを回収することができる。具体的には、例えばスズ含有量１０ppm未満の金属インジウムを回収することができる。なお、上記卑金属としては亜鉛またはアルミニウムまたは鉄の少なくとも一種を用いることができる。 [Second tin removal process]
While maintaining the pH of the filtrate from which the tin oxalate precipitate has been separated from 0.5 to 2, indium, zinc or aluminum is added to reduce and precipitate a small amount of tin remaining in the filtrate. Liquid separation and proceed with tin removal. Sponge-like metal indium with a remarkably low tin content can be recovered by adding a metal lower than indium to the tin removal solution from which the tin sponge has been removed to reduce and deposit indium. Specifically, for example, metal indium having a tin content of less than 10 ppm can be recovered. In addition, as said base metal, at least 1 type of zinc, aluminum, or iron can be used.

以下、本発明の実施例を比較例と共に示す。なお、各例において、澱物および金属インジウムの含有成分量はＩＣＰによって測定した。結果を表１に示した。 Examples of the present invention are shown below together with comparative examples. In each example, the content of starch and metal indium was measured by ICP. The results are shown in Table 1.

〔実施例１〕
スポンジ状のＩｎ−Ｓｎ合金（In10wt％、Sn90wt％）１００ｇを塩酸０.５L（濃度６mol/L）に混合し、８０℃に加熱して溶解させた。この塩酸溶解液にシュウ酸アンモニウム一水和物を粉末状で１２０ｇ添加し、さらに苛性ソーダを添加して溶解液のｐＨを１.２に調整し、生成した沈澱を濾過して分離した。この澱物の乾燥重量は１４８ｇであり、スズ含有量５８wt％のスズ主体の澱物であった。一方、シュウ酸濾液にはスズが５ｇ/L程残留しており、これにインジウムメタルを浸漬してスズを還元析出させて濾過分離した。この脱スズ濾液中のスズ濃度は１ppm以下であった。この脱スズ濾液に亜鉛を添加してインジウムを還元析出させた。これを回収して乾燥し、スポンジ状の金属インジウムを得た。この金属インジウムのスズ含有量は１０ppm以下であった。 [Example 1]
100 g of a sponge-like In—Sn alloy (In 10 wt%, Sn 90 wt%) was mixed with 0.5 L of hydrochloric acid (concentration 6 mol / L) and dissolved by heating to 80 ° C. To this hydrochloric acid solution, 120 g of ammonium oxalate monohydrate was added in powder form, caustic soda was added to adjust the pH of the solution to 1.2, and the resulting precipitate was separated by filtration. The dry weight of this starch was 148 g, and it was a tin-based starch having a tin content of 58 wt%. On the other hand, about 5 g / L of tin remained in the oxalic acid filtrate, and indium metal was immersed in this to reduce and precipitate tin, followed by filtration and separation. The tin concentration in the tin removal filtrate was 1 ppm or less. Zinc was added to the tin removal filtrate to reduce and deposit indium. This was recovered and dried to obtain sponge-like metal indium. The tin content of the metal indium was 10 ppm or less.

〔実施例２〜４〕
溶解条件、シュウ酸化合物、脱スズでの使用金属を表１に示すように調整した以外は実施例１と同様にして金属インジウムを回収した。この結果を表１に示した。回収したインジウムスポンジ中のスズ含有量は何れも１０ppm以下であった。 [Examples 2 to 4]
Indium metal was recovered in the same manner as in Example 1 except that the dissolution conditions, the oxalic acid compound, and the metal used in tin removal were adjusted as shown in Table 1. The results are shown in Table 1. The tin content in the recovered indium sponge was 10 ppm or less.

〔比較例１〜３〕
比較例１は硝酸を使用した例である。硝酸を用いることによってIn-Snメタル溶解液中のSn溶解量は少なくなっているが、シュウ酸スズ沈殿工程でのシュウ酸スズの生成が悪く、従ってシュウ酸スズを濾過分離した濾液中のスズ濃度が高く、次の脱スズ工程で使用するインジウムメタルを多量に必要とし、原料中に含有されるインジウムよりも多い量を使用している。また、インジウム回収工程ではインジウムのスポンジが得られなかった。
比較例２は溶解時の温度を３０℃にした以外は実施例３と同様の条件で溶解した例であり、In-Snメタルの溶解が進行しない。
比較例３は実施例４と同様の浸出条件とし、シュウ酸スズの生成工程（第一脱スズ工程）を省略したものである。第二脱スズ工程で使用する亜鉛末添加量を実施例１と同じに液中のスズ濃度の１.２倍にしたものの脱スズが進行せず、液中に残留するスズ量が多い。また得られるスポンジ品位も悪く、かつ回収されるインジウムの極端に低い。 [Comparative Examples 1-3]
Comparative Example 1 is an example using nitric acid. Although the amount of Sn dissolved in the In-Sn metal solution is reduced by using nitric acid, the formation of tin oxalate in the tin oxalate precipitation process is poor, so the tin in the filtrate from which tin oxalate was filtered and separated. It has a high concentration, requires a large amount of indium metal to be used in the next tin removal step, and uses a larger amount than indium contained in the raw material. Also, no indium sponge was obtained in the indium recovery process.
Comparative Example 2 is an example in which dissolution was performed under the same conditions as in Example 3 except that the temperature during dissolution was 30 ° C., and dissolution of In—Sn metal did not proceed.
Comparative Example 3 is a leaching condition similar to that of Example 4 and omits the tin oxalate production step (first tin removal step). Although the addition amount of zinc powder used in the second tin removal step was 1.2 times the tin concentration in the liquid as in Example 1, the tin removal did not proceed and the amount of tin remaining in the liquid was large. Also, the sponge quality obtained is poor and the recovered indium is extremely low.

Figure 2007009274
Figure 2007009274

本発明の回収方法の概略を示す工程図Process drawing which shows the outline of the collection | recovery method of this invention

Claims (4)

インジウムとスズを金属形態で含有するインジウム−スズ含有物を塩酸、硫酸、または塩酸と硫酸の混酸に溶解し、この溶解液にシュウ酸化合物を添加してシュウ酸スズ沈澱を生成させ、このシュウ酸スズ沈澱を固液分離した濾液にインジウムまたは亜鉛またはアルミニウムを添加して濾液に残留するスズを析出させて固液分離し、この脱スズ濾液に卑金属を添加してインジウムを析出させ、スポンジ状の金属インジウムを回収することを特徴とするインジウムの回収方法。
An indium-tin-containing material containing indium and tin in a metal form is dissolved in hydrochloric acid, sulfuric acid, or a mixed acid of hydrochloric acid and sulfuric acid, and an oxalic acid compound is added to the solution to form a tin oxalate precipitate. Indium, zinc or aluminum is added to the filtrate obtained by solid-liquid separation of the tin oxide precipitate to precipitate the remaining tin in the filtrate and solid-liquid separation is performed, and base metal is added to the detinized filtrate to precipitate indium, resulting in a sponge-like form. A method for recovering indium, comprising recovering metal indium.
請求項１の方法において、Ｉｎ−Ｓｎ合金を出発原料として用いるインジウムの回収方法。
The method of claim 1, wherein an In-Sn alloy is used as a starting material.
Ｉｎ−Ｓｎ合金を、塩酸または硫酸または塩酸と硫酸の混酸に溶解し、この溶解液にシュウ酸化合物とアルカリ化合物とを添加し、ｐＨ０.５〜３の液性下でシュウ酸スズ沈澱を生成させ、シュウ酸スズ沈澱を固液分離した濾液にｐＨ０.５〜２の液性下でインジウムまたは亜鉛またはアルミニウムを添加して濾液に残留するスズを析出させて固液分離し、この脱スズ濾液に亜鉛またはアルミニウムまたは鉄の少なくとも一種を添加してインジウムを析出させ、スズ含有量５ppm未満の金属インジウムを回収することを特徴とする方法。
An In-Sn alloy is dissolved in hydrochloric acid or sulfuric acid or a mixed acid of hydrochloric acid and sulfuric acid, and an oxalic acid compound and an alkali compound are added to the solution to produce a tin oxalate precipitate at a pH of 0.5 to 3 Then, indium, zinc or aluminum was added to the filtrate obtained by solid-liquid separation of the tin oxalate precipitate, and the tin remaining in the filtrate was precipitated under a liquid state of pH 0.5 to 2, and the solid-liquid separation was performed. And adding at least one of zinc, aluminum, or iron to precipitate indium, and recovering metal indium having a tin content of less than 5 ppm.
シュウ酸化合物としてシュウ酸、シュウ酸アンモニウム、アルカリ金属シュウ酸塩の少なくとも一種を用いる請求項１〜３の何れかに記載するインジウムの回収方法。 The method for recovering indium according to any one of claims 1 to 3, wherein at least one of oxalic acid, ammonium oxalate, and alkali metal oxalate is used as the oxalic acid compound.
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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
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
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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
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
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
JP2009191309A (en) * 2008-02-14 2009-08-27 Sumitomo Metal Mining Co Ltd Method for collecting crude indium
WO2009146485A1 (en) * 2008-06-06 2009-12-10 The University Of Sydney Multi-stage leaching process
KR100932706B1 (en) 2009-08-31 2009-12-21 (주)티에스엠 Method for recycling indium from indium containing waste solution
JP2012052215A (en) * 2010-08-31 2012-03-15 Jx Nippon Mining & Metals Corp Method for collecting indium
CN104451205A (en) * 2013-09-12 2015-03-25 汉能新材料科技有限公司 Indium extraction method capable of efficiently removing iron
CN105483389A (en) * 2016-01-13 2016-04-13 云南大学 Leaching method for indium in waste liquid crystal panel and leaching agent
KR20200004556A (en) * 2018-07-04 2020-01-14 엘에스피주식회사 Production of High-purity Indium Oxide from Waste ITO target
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