JP2002069544A - Method for recovering indium - Google Patents
Method for recovering indiumInfo
- Publication number
- JP2002069544A JP2002069544A JP2000256759A JP2000256759A JP2002069544A JP 2002069544 A JP2002069544 A JP 2002069544A JP 2000256759 A JP2000256759 A JP 2000256759A JP 2000256759 A JP2000256759 A JP 2000256759A JP 2002069544 A JP2002069544 A JP 2002069544A
- Authority
- JP
- Japan
- Prior art keywords
- indium
- recovering
- adjusted
- solution
- scrap
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、インジウム−錫
酸化物（ＩＴＯ）スパッタリングターゲットの製造時又
は使用後に発生する高純度酸化インジウム含有スクラッ
プからインジウムを回収する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering indium from scrap containing high-purity indium oxide generated during or after manufacturing an indium-tin oxide (ITO) sputtering target.
【０００２】[0002]
【従来の技術】近年、インジウム−錫酸化物（ＩＴＯ）
スパッタリングターゲットは液晶表示装置の透明導電性
薄膜やガスセンサーなどに広く使用されているが、多く
の場合スパッタリング法による薄膜形成手段を用いて基
板等の上に薄膜が形成されている。このスパッタリング
法による薄膜形成手段は優れた方法であるが、スパッタ
リングターゲットを用いて、例えば透明導電性薄膜を形
成していくと、該ターゲットは均一に消耗していく訳で
はない。このターゲットの一部の消耗が激しい部分を一
般にエロージョン部と呼んでいるが、このエロージョン
部の消耗が進行し、ターゲットを支持するバッキングプ
レートが剥き出しになる直前までスパッタリング操作を
続行する。そして、その後は新しいターゲットと交換し
ている。したがって、使用済みのスパッタリングターゲ
ットには多くの非エロージョン部、すなわち未使用のタ
ーゲット部分が残存することになり、これらは全てスク
ラップとなる。また、ＩＴＯスパッタリングターゲット
の製造時においても、研磨粉や切削粉からスクラップが
発生する。2. Description of the Related Art In recent years, indium-tin oxide (ITO) has been developed.
Sputtering targets are widely used for transparent conductive thin films of liquid crystal display devices, gas sensors, and the like. In many cases, thin films are formed on a substrate or the like using a thin film forming means by a sputtering method. This thin film forming means by the sputtering method is an excellent method. However, when a transparent conductive thin film is formed using a sputtering target, for example, the target is not consumed uniformly. The part of the target that is heavily consumed is generally called an erosion part. The sputtering operation is continued until the erosion part is consumed and the backing plate supporting the target is exposed. And then exchange for a new target. Therefore, many non-erosion portions, that is, unused target portions remain in the used sputtering target, and all of them become scrap. Also, during the production of the ITO sputtering target, scrap is generated from the polishing powder and the cutting powder.
【０００３】ＩＴＯスパッタリングターゲット材料には
高純度材が使用されており、価格も高いので、一般にこ
のようなスクラップ材からインジウムを回収することが
行われている。このインジウム回収方法として、従来酸
溶解法、イオン交換法、溶媒抽出法などの湿式精製を組
み合わせた方法が用いられている。例えば、ＩＴＯスク
ラップを洗浄及び粉砕後、硝酸に溶解し、溶解液に硫化
水素を通して、亜鉛、錫、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である。しか
し、この方法によって得られた水酸化インジウムはろ過
性が悪く操作に長時間を要し、Ｓｉ、Ａｌ等の不純物が
多く、また生成する水酸化インジウムはその中和条件及
び熟成条件等により、粒径や粒度分布が変動するため、
その後ＩＴＯターゲットを製造する際に、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っ
た。[0003] Since a high-purity material is used as an ITO sputtering target material and its cost is high, indium is generally recovered from such scrap material. As this indium recovery method, a method combining wet purification such as an acid dissolution method, an ion exchange method, and a solvent extraction method has been conventionally used. For example, an ITO scrap is washed and pulverized, then dissolved in nitric acid, hydrogen sulfide is passed through the solution to precipitate and remove impurities such as zinc, tin, lead, and copper as sulfide, and then neutralized by adding ammonia thereto. And indium hydroxide. However, indium hydroxide obtained by this method has poor filterability and requires a long time for operation, has many impurities such as Si and Al, and indium hydroxide to be generated depends on its neutralizing conditions and aging conditions. Because the particle size and particle size distribution fluctuate,
Thereafter, when manufacturing the ITO target, there is a problem that the characteristics of the ITO target cannot be stably maintained.
【０００４】このようなことから、本発明者は先に、Ｉ
ＴＯスクラップ等の酸化インジウムを含有する物質を、
予め７５０〜１２００°Ｃで還元性ガスにより還元して
金属インジウムとした後、該インジウムを電解精製する
インジウムの回収方法を提案した（特開平７−１４５４
３２号公報）。これによれば、高純度のインジウムを効
率良く安定して回収することが可能となった。しかし、
還元されたメタルはインジウム−錫合金となっている。
このインジウム−錫合金をアノードとしてインジウムを
電解精製すると、錫はアノードスライムとなって浴を懸
濁させ、精製されたはずのインジウム中に不純物して混
入するという問題があるのでさらに改善が必要であっ
た。[0004] In view of the above, the present inventor has previously described I
A substance containing indium oxide, such as TO scrap,
A method for recovering indium has been proposed in which metal indium is previously reduced at 750 to 1200 ° C. with a reducing gas to electrolytically purify the indium (JP-A-7-1454).
No. 32). According to this, high-purity indium can be efficiently and stably recovered. But,
The reduced metal is an indium-tin alloy.
If this indium-tin alloy is used as an anode for electrolytic refining of indium, tin becomes an anode slime, suspending the bath, and there is a problem that impurities are mixed into the purified indium. there were.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記の問題
を解決するために、ＩＴＯスパッタリングターゲットの
製造時又は使用後に発生する高純度酸化インジウム含有
スクラップからインジウムを効率良く回収する方法を提
供することにある。SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides a method for efficiently recovering indium from high-purity indium oxide-containing scrap generated during or after the production of an ITO sputtering target. It is in.
【０００６】[0006]
【課題を解決するための手段】本発明は、 １． ＩＴＯインジウム含有スクラップを塩酸で溶解し
て塩化インジウム溶液とし、該溶液とする工程、該塩化
インジウム溶液に水酸化ナトリウム水溶液を添加してス
クラップ中に含有する錫を水酸化錫として除去する工
程、該水酸化錫を除去した後液から亜鉛によりインジウ
ムを置換、回収することを特徴とするインジウムの回収
方法 ２． 置換、回収したスポンジインジウムを固体の水酸
化ナトリウムと共に溶解して粗インジウムメタルを作製
した後、さらに該粗インジウムメタルを電解精製し、高
純度インジウムを得ることを特徴とするインジウムの回
収方法 ３． ＩＴＯインジウム含有スクラップを塩酸で溶解す
る際に、ＩＴＯインジウム含有スクラップ１００ｋｇに
対し、塩酸量を３００〜６００Ｌとし、溶解温度を１０
０〜１１０°Ｃとすることを特徴とする上記１又は２に
記載するインジウムの回収方法 ４． 水酸化ナトリウム水溶液を添加してｐＨを１．５
〜２．０に調整し、スクラップ中に含有する錫を水酸化
錫として除去することを特徴とする上記１〜３のそれぞ
れに記載のインジウムの回収方法 ５． 塩化インジウム溶液のｐＨを１．５〜２．５に、
液温度を５〜５０°Ｃに調製することを特徴とする上記
１〜４のそれぞれに記載のインジウムの回収方法 ６． 塩化インジウム溶液のｐＨを１．７〜２．０に、
液温度を３０〜４０°Ｃに調製することを特徴とする上
記１〜４のそれぞれに記載のインジウムの回収方法 ７． 亜鉛板を用いてインジウムを置換、回収すること
を特徴とする上記１〜６のそれぞれに記載のインジウム
の回収方法 ８． 粗インジウムメタルをアノードとし、硫酸浴を用
いて、ｐＨ１．８〜２．０、電解精製液中の塩素イオン
濃度を２０〜３０ｇ／Ｌに調製し、電解精製することを
特徴とする上記１〜７のそれぞれに記載のインジウムの
回収方法 ９． 塩素イオン源として、塩酸又は塩化ナトリウム、
塩化カリウム等のアルカリ金属塩化物及び塩化インジウ
ムを使用することを特徴とする上記８に記載するインジ
ウムの回収方法 １０． 電解液中のインジウム濃度を４５〜５５ｇ／Ｌ
に調製することを特徴とする上記８又は９に記載するイ
ンジウムの回収方法 １１． 電解温度を２５〜５０°Ｃに調製することを特
徴とする上記８〜１０のそれぞれに記載するインジウム
の回収方法 を提供する。The present invention provides: Dissolving the indium-containing ITO scrap with hydrochloric acid to form an indium chloride solution and preparing the solution; and adding an aqueous sodium hydroxide solution to the indium chloride solution to remove tin contained in the scrap as tin hydroxide. 1. A method for recovering indium, which comprises replacing and recovering indium with zinc from a liquid after removing tin hydroxide. 2. A method for recovering indium, which comprises dissolving the replaced and recovered sponge indium together with solid sodium hydroxide to produce a crude indium metal, and further electrolytically refining the crude indium metal to obtain high-purity indium. When dissolving the ITO indium-containing scrap with hydrochloric acid, the amount of hydrochloric acid is set to 300 to 600 L and the dissolution temperature is set at 10 to 100 kg of the ITO indium-containing scrap.
3. The method for recovering indium according to 1 or 2 above, wherein the temperature is 0 to 110 ° C. The pH is adjusted to 1.5 by adding an aqueous sodium hydroxide solution.
4. The method for recovering indium according to any one of the above items 1 to 3, wherein the tin is adjusted to 2.0 and tin contained in the scrap is removed as tin hydroxide. The pH of the indium chloride solution to 1.5-2.5,
5. The method for recovering indium according to any one of the above items 1 to 4, wherein the liquid temperature is adjusted to 5 to 50 ° C. The pH of the indium chloride solution to 1.7-2.0,
6. The method for recovering indium according to any one of the above items 1 to 4, wherein the liquid temperature is adjusted to 30 to 40 ° C. 7. The method for recovering indium according to any one of the above items 1 to 6, wherein indium is replaced and recovered using a zinc plate. The crude indium metal is used as an anode, the pH is adjusted to 1.8 to 2.0 using a sulfuric acid bath, and the chloride ion concentration in the electrolytically purified solution is adjusted to 20 to 30 g / L. 8. The method for recovering indium described in each of 7. As a chloride ion source, hydrochloric acid or sodium chloride,
9. The method for recovering indium as described in 8 above, wherein an alkali metal chloride such as potassium chloride or the like and indium chloride are used. The indium concentration in the electrolyte is 45 to 55 g / L
10. The method for recovering indium as described in 8 or 9 above, wherein the indium is prepared. The method for recovering indium according to any one of the above items 8 to 10, wherein the electrolysis temperature is adjusted to 25 to 50 ° C.
【０００７】[0007]
【発明の実施の形態】本発明は、ＩＴＯターゲットの研
磨粉等のインジウム含有スクラップを塩酸で溶解する。
この場合、ＩＴＯインジウム含有スクラップ１００ｋｇ
に対して塩酸量を３００Ｌ〜６００Ｌとし、温度１００
〜１１０°Ｃで溶解する。この溶解温度は沸騰状態にあ
る。溶解時間は約３〜５時間程度であり、適宜調節す
る。塩酸量は３００Ｌ〜６００Ｌとする。３００Ｌは反
応当量であり、６００Ｌを超えて添加しても特に反応が
促進するわけではないので、無駄である。上記塩酸量に
調製し、かつ温度１００〜１１０°Ｃで溶解することに
より、未溶解残を極力少なくできる。次に、スクラップ
中の錫を水酸化錫として中和除去するため、水酸化ナト
リウム水溶液等を用いて、塩化インジウム溶液のｐＨ調
製を行い、塩化インジウム溶液のｐＨを１．５〜２．５
とする。水酸化ナトリウム水溶液以外に、水酸化カリウ
ムを使用することもできる。ｐＨを１．５〜２．５とす
る理由は、ｐＨが１．５未満であると錫の水酸化物は完
全に生成せず、また２．５を超えると水酸化インジウム
（Ｉｎ（ＯＨ）３）が生成して好ましくないからであ
る。好ましくは、塩化インジウム溶液のｐＨを１．７〜
２．０に調節する。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, scrap containing indium such as polishing powder of an ITO target is dissolved with hydrochloric acid.
In this case, 100 kg of ITO indium-containing scrap
The amount of hydrochloric acid is set to 300 L to 600 L, and the temperature is 100
Dissolve at ~ 110 ° C. This melting temperature is in the boiling state. The dissolution time is about 3 to 5 hours, and is appropriately adjusted. The amount of hydrochloric acid is 300 L to 600 L. 300 L is a reaction equivalent, and if added in excess of 600 L, the reaction is not particularly accelerated, so it is useless. By adjusting to the above hydrochloric acid amount and dissolving at a temperature of 100 to 110 ° C., the undissolved residue can be reduced as much as possible. Next, in order to neutralize and remove tin in the scrap as tin hydroxide, the pH of the indium chloride solution is adjusted using an aqueous sodium hydroxide solution or the like, and the pH of the indium chloride solution is adjusted to 1.5 to 2.5.
And In addition to the aqueous sodium hydroxide solution, potassium hydroxide can also be used. The reason for setting the pH to 1.5 to 2.5 is that when the pH is less than 1.5, tin hydroxide is not completely formed, and when the pH exceeds 2.5, indium hydroxide (In (OH) This is because 3 ) is not preferred. Preferably, the pH of the indium chloride solution is from 1.7 to
Adjust to 2.0.
【０００８】次に、この水酸化錫を濾過除去する。これ
を亜鉛による置換用原料とする。この時の塩化インジウ
ム溶液の液温度を５〜５０°Ｃに調整する。塩化インジ
ウム溶液の液温度を５〜５０°Ｃに調整する理由は、５
°Ｃ未満では反応が遅く、また５０°Ｃを超えると水分
蒸発量が増大して液濃度が不安定になり効率的な反応を
行うことができないからである。好ましくは塩化インジ
ウム溶液の液温度を３０〜４０°Ｃに調整する。塩化イ
ンジウム溶液を亜鉛板等を使用してインジウムを置換す
る。この場合、約１６時間放置して置くだけでよい。Next, the tin hydroxide is removed by filtration. This is used as a raw material for replacement with zinc. At this time, the temperature of the indium chloride solution is adjusted to 5 to 50 ° C. The reason for adjusting the temperature of the indium chloride solution to 5 to 50 ° C is as follows.
If the temperature is lower than 50 ° C., the reaction is slow, and if the temperature exceeds 50 ° C., the amount of water evaporation increases, the liquid concentration becomes unstable, and an efficient reaction cannot be performed. Preferably, the liquid temperature of the indium chloride solution is adjusted to 30 to 40 ° C. The indium chloride solution is replaced with indium using a zinc plate or the like. In this case, it is only necessary to leave it for about 16 hours.
【０００９】置換後、固液分離、水洗、乾燥し、スポン
ジインジウムを得る。さらに、この回収したスポンジイ
ンジウムを固体の水酸化ナトリウムと共に溶融して粗イ
ンジウムメタルを作製する。次に、このインジウムメタ
ルを溶解、鋳造して電解精製用のアノードとする。さら
に、このインジウムメタルアノードについて、硫酸浴を
用い、ｐＨ１．８〜２．０、該塩素イオン濃度を２０〜
３５ｇ／Ｌに調整し、電解精製して高純度インジウムを
回収する。前記塩素イオン源として、塩酸又は塩化ナト
リウム、塩化カリウム等のアルカリ金属塩化物及び塩化
インジウムを使用することができる。インジウムの電解
精製の際に、電解精製液中に塩素イオンを入れるのは、
樹枝状電着物（デンドライト）の生成を防止し、この結
果電極間のショートを抑制して、電解精製によるインジ
ウムの回収における電流効率の低下を効果的に防止する
ことができるからである。また電解温度を２５〜５０°
Ｃに調整し、電解液中のインジウム濃度を４５〜５５ｇ
／Ｌに調製するのが望ましい。このように、電解温度を
２５〜５０°Ｃに調整し、電解液中のインジウム濃度を
４５〜５５ｇ／Ｌに調製するのは、４５ｇ／Ｌ未満では
電流効率が悪くなり、水素の発生が多くなるので好まし
くないからである。また、５５ｇ／Ｌを超えても電解に
は特に問題ないが、系内残が増加するという問題がある
ので、５５ｇ／Ｌ以下とすることが望ましい。After replacement, solid-liquid separation, washing with water and drying are performed to obtain sponge indium. Further, the recovered sponge indium is melted together with solid sodium hydroxide to produce a crude indium metal. Next, this indium metal is melted and cast to form an anode for electrolytic refining. Further, for this indium metal anode, using a sulfuric acid bath, the pH was 1.8 to 2.0, and the chlorine ion concentration was 20 to
It is adjusted to 35 g / L and electrolytically purified to recover high-purity indium. As the chlorine ion source, hydrochloric acid or alkali metal chlorides such as sodium chloride and potassium chloride and indium chloride can be used. During the electrolytic refining of indium, chloride ions are put into the electrolytic refining solution because
This is because the formation of dendritic deposits (dendrites) can be prevented, and as a result, a short circuit between the electrodes can be suppressed, and a decrease in current efficiency in the recovery of indium by electrolytic refining can be effectively prevented. The electrolysis temperature is 25-50 °
C, and adjust the indium concentration in the electrolyte solution to 45 to 55 g.
/ L is desirable. As described above, adjusting the electrolysis temperature to 25 to 50 ° C. and adjusting the indium concentration in the electrolyte solution to 45 to 55 g / L is because the current efficiency is deteriorated when the indium concentration is less than 45 g / L, and the generation of hydrogen is increased. This is because it is not preferable. Further, even if it exceeds 55 g / L, there is no particular problem in the electrolysis, but there is a problem that the residue in the system increases.
【００１０】電解装置として特別なものは必要としな
い。例えば精製するインジウムをアノードとし、カソー
ド母板としてチタン板等を用いて電解すれば良い。アノ
ード中の不純物の内インジウムより貴なもの、例えば錫
などはスライムとなって沈殿し、インジウムより卑なも
のは電解液中に溶解し、カソードには析出してこない。
この場合、析出物へのスライムの混入を避けるためアノ
ードとカソードの間に隔膜を設けるのが望ましい。電解
液中に、にかわ、ゼラチン、ＰＥＧ等の界面活性剤を添
加して、さらに樹枝状析出物の量を低下させることがで
きる。電解液のＰＨは１．０〜２．０に調整するのが良
い。ＰＨが１．０未満であると水素の発生が多くなり、
電流効率が低下するため好ましくない。また、ＰＨが
２．０を超えるとインジウムが水酸化物を作り沈殿する
ので好ましくない。より好適な範囲はＰＨ１．５〜１．
８である。[0010] No special electrolytic device is required. For example, electrolysis may be performed using indium to be purified as an anode and a titanium plate or the like as a cathode mother plate. Of the impurities in the anode, those noble than indium, such as tin, precipitate as slime, and those nobler than indium dissolve in the electrolytic solution and do not precipitate on the cathode.
In this case, it is desirable to provide a diaphragm between the anode and the cathode in order to avoid mixing of slime into the precipitate. Surfactants such as glue, gelatin, and PEG can be added to the electrolyte to further reduce the amount of dendritic precipitates. The pH of the electrolyte is preferably adjusted to 1.0 to 2.0. If the pH is less than 1.0, the generation of hydrogen increases,
It is not preferable because the current efficiency decreases. On the other hand, when the pH exceeds 2.0, indium forms a hydroxide and precipitates, which is not preferable. A more preferred range is PH 1.5-1.
8
【００１１】電流密度は０．１〜２．０Ａ／ｄｍ２に調
整することが望ましい。電流密度が０．１Ａ／ｄｍ２未
満であると、生産効率が落ちる。また、逆に電流密度が
２．０Ａ／ｄｍ２を超えると、水素ガス発生が多くなり
電着せず好ましくない。また、電解温度は１０〜７５°
Ｃに調整して電解することが望ましい。電解温度１０°
Ｃ未満であると電流効率が低下し好ましくない。逆に電
解温度が７５°Ｃを超えると電解液の蒸発が多くなり、
電解液中のインジウム濃度が変動するため好ましくな
い。より好ましい電解温度は２５〜５０°Ｃである。以
上の電解条件により、ショートの原因となる樹枝状の析
出を防止することができ、それによって電流効率の低下
を防止し、かつ電解精製により効率よくインジウムを回
収することができる。It is desirable to adjust the current density to 0.1 to 2.0 A / dm 2 . If the current density is less than 0.1 A / dm 2 , the production efficiency decreases. On the other hand, when the current density exceeds 2.0 A / dm 2 , the generation of hydrogen gas increases, and electrodeposition is not performed, which is not preferable. The electrolysis temperature is 10 to 75 °.
It is desirable to perform electrolysis while adjusting to C. Electrolysis temperature 10 °
If it is less than C, the current efficiency decreases, which is not preferable. Conversely, when the electrolysis temperature exceeds 75 ° C, the evaporation of the electrolyte increases,
It is not preferable because the indium concentration in the electrolytic solution fluctuates. A more preferred electrolysis temperature is 25 to 50 ° C. The above electrolysis conditions can prevent dendritic precipitation that causes a short circuit, thereby preventing a decrease in current efficiency and efficiently recovering indium by electrolytic purification.
【００１２】[0012]
【実施例】次に、実施例について説明する。なお、本実
施例は発明の一例を示すためのものであり、本発明はこ
れらの実施例に制限されるものではない。すなわち、本
発明の技術思想に含まれる他の態様及び変形を含むもの
である。ＩＴＯインジウム含有スクラップ原料として、
酸化インジウム−酸化錫（ＩＴＯスクラップ）２ｋｇを
使用した。このスクラップ中、Ｉｎは７３．６ｗｔ％、
Ｓｎは８．６ｗｔ％であった。このスクラップ原料に、
濃塩酸を１０リットル添加し、１１０°Ｃで４時間加熱
した。液は沸騰状態にあった。溶解後、約６リットルと
なった液に、６．５Ｎ水酸化ナトリウム３．４リットル
を添加し、ｐＨ２．０まで中和し水酸化錫を生成させ
た。Next, an embodiment will be described. It should be noted that the present embodiment is merely an example of the present invention, and the present invention is not limited to these embodiments. That is, it includes other aspects and modifications included in the technical idea of the present invention. As a raw material for scrap containing ITO indium,
2 kg of indium oxide-tin oxide (ITO scrap) was used. In this scrap, In was 73.6 wt%,
Sn was 8.6 wt%. In this scrap material,
10 L of concentrated hydrochloric acid was added, and the mixture was heated at 110 ° C. for 4 hours. The liquid was boiling. After dissolution, 3.4 L of 6.5 N sodium hydroxide was added to the solution which became about 6 L, and neutralized to pH 2.0 to generate tin hydroxide.
【００１３】次に、これを濾過し、残渣（水酸化錫）は
スクラップとし、濾液約１０リットルを入手した。これ
に水２０リットルを加え、還元液約３０リットルに調整
した。この時のＩｎ濃度は４８．６ｇ／Ｌであった。こ
の還元液に１２ｃｍ×１５ｃｍの亜鉛板１１枚を浸漬
し、１６時間放置した。この時の亜鉛板の面積は３９６
０ｃｍ２であった。この後、固液分離した。この時の廃
液中にはＺｎ４６．２ｇ／Ｌ、Ｉｎ０．２ｇ／Ｌが含ま
れていた。これを水洗、乾燥した。Ｉｎ中のＺｎ品位は
４６０ｐｐｍであった。これを溶解し鋳造して電解精製
用アノード１４２１ｇが得られた。次に、硫酸浴中で電
解精製を行った。電解条件は次の通りである。 ｐＨ１．８〜２．０ 塩素２０〜３０ｇ／Ｌ Ｉｎ濃度４５〜５５ｇ／Ｌ 温度４０°Ｃ これによって、得られた精製インジウムの錫品位は＜１
０ｐｐｍ（重量）であった。以上から、酸化インジウム
−酸化錫（ＩＴＯ）スクラップの不純物としての大半を
占める錫を除去することが可能であり、純度の高いイン
ジウムを回収することができた。Next, this was filtered, and the residue (tin hydroxide) was scrapped to obtain about 10 liters of filtrate. To this, 20 liters of water was added to adjust the reducing solution to about 30 liters. At this time, the In concentration was 48.6 g / L. Eleven zinc plates of 12 cm × 15 cm were immersed in this reducing solution and left for 16 hours. The area of the zinc plate at this time is 396
0 cm 2 . Thereafter, solid-liquid separation was performed. The waste liquid at this time contained 46.2 g / L of Zn and 0.2 g / L of In. This was washed with water and dried. The Zn grade in In was 460 ppm. This was melted and cast to obtain 1421 g of an anode for electrolytic refining. Next, electrolytic purification was performed in a sulfuric acid bath. The electrolysis conditions are as follows. pH 1.8-2.0 Chlorine 20-30 g / L In concentration 45-55 g / L Temperature 40 ° C. Thus, the tin quality of the obtained purified indium is <1.
It was 0 ppm (weight). From the above, it was possible to remove tin occupying most of the impurities in the indium oxide-tin oxide (ITO) scrap, and to recover indium with high purity.
【００１４】[0014]
【発明の効果】本発明は、ＩＴＯスパッタリングターゲ
ットの製造時又は使用後に発生する高純度酸化インジウ
ム含有スクラップからインジウムを能率良く回収するこ
とができるという優れた効果を有する。The present invention has an excellent effect that indium can be efficiently recovered from high-purity indium oxide-containing scrap generated during or after the production of an ITO sputtering target.
【図１】インジウムの回収工程図である。FIG. 1 is a drawing showing a recovery process of indium.
───────────────────────────────────────────────────── 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） Ｃ２２Ｂ 7/00 Ｃ２２Ｂ 3/00 Ａ Ｃ２５Ｃ 1/22 Ｕ 7/06 ３０１ Ｑ // Ｃ２２Ｂ 25/00 25/04 Ｆターム(参考） 4K001 AA15 AA24 BA22 DA14 DB04 DB18 DB21 DB23 4K058 AA23 BA07 BB03 CA04 CA05 CA13 CA17 EB16 EC04 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C22B 7/00 C22B 3/00 A C25C 1/22 U 7/06 301 Q // C22B 25/00 25 / 04 F term (reference) 4K001 AA15 AA24 BA22 DA14 DB04 DB18 DB21 DB23 4K058 AA23 BA07 BB03 CA04 CA05 CA13 CA17 EB16 EC04
Claims (11)
で溶解して塩化インジウム溶液とする工程、該塩化イン
ジウム溶液に水酸化ナトリウム水溶液を添加してスクラ
ップ中に含有する錫を水酸化錫として除去する工程、該
水酸化錫を除去した後液から亜鉛によりインジウムを置
換、回収する工程からなることを特徴とするインジウム
の回収方法。A step of dissolving the indium-containing ITO scrap with hydrochloric acid to form an indium chloride solution; a step of adding an aqueous sodium hydroxide solution to the indium chloride solution to remove tin contained in the scrap as tin hydroxide; A method for recovering indium, comprising a step of replacing and recovering indium with zinc from a liquid after removing the tin hydroxide.
の水酸化ナトリウムと共に溶解して粗インジウムメタル
を作製した後、さらに該粗インジウムメタルを電解精製
し、高純度インジウムを得ることを特徴とする請求項１
記載のインジウムの回収方法。2. The method according to claim 1, wherein the sponge indium that has been replaced and recovered is dissolved together with solid sodium hydroxide to produce a crude indium metal, and the crude indium metal is further electrolytically purified to obtain high-purity indium. 1
The method for recovering indium according to the above.
で溶解する際に、ＩＴＯインジウム含有スクラップ１０
０ｋｇに対し、塩酸量を３００〜６００Ｌとし、溶解温
度を１００〜１１０°Ｃとすることを特徴とする請求項
１又は２に記載するインジウムの回収方法。3. When dissolving the ITO indium-containing scrap with hydrochloric acid, the ITO indium-containing scrap 10
The method for recovering indium according to claim 1 or 2, wherein the amount of hydrochloric acid is set to 300 to 600 L and the dissolution temperature is set to 100 to 110 ° C for 0 kg.
を１．５〜２．０に調整し、スクラップ中に含有する錫
を水酸化錫として除去することを特徴とする請求項１〜
３のそれぞれに記載のインジウムの回収方法。4. An aqueous solution of sodium hydroxide is added to adjust pH.
Is adjusted to 1.5 to 2.0, and tin contained in the scrap is removed as tin hydroxide.
3. The method for recovering indium according to 3 above.
２．５に、液温度を５〜５０°Ｃに調製することを特徴
とする請求項１〜４のそれぞれに記載のインジウムの回
収方法。5. The pH of the indium chloride solution is adjusted to 1.5 to 5.
The method for recovering indium according to any one of claims 1 to 4, wherein the liquid temperature is adjusted to 5 to 50 ° C in 2.5.
２．０に、液温度を３０〜４０°Ｃに調製することを特
徴とする請求項１〜４のそれぞれに記載のインジウムの
回収方法。6. The pH of the indium chloride solution is from 1.7 to 1.7.
The method for recovering indium according to any one of claims 1 to 4, wherein the liquid temperature is adjusted to 2.0 and the liquid temperature is adjusted to 30 to 40 ° C.
することを特徴とする請求項１〜６のそれぞれに記載の
インジウムの回収方法。7. The method for recovering indium according to claim 1, wherein indium is replaced and recovered using a zinc plate.
酸浴を用いて、ｐＨ１．８〜２．０、電解精製液中の塩
素イオン濃度を２０〜３０ｇ／Ｌに調製し、電解精製す
ることを特徴とする請求項１〜７のそれぞれに記載のイ
ンジウムの回収方法。8. The method according to claim 1, wherein the crude indium metal is used as an anode, the pH is adjusted to 1.8 to 2.0, and the chloride ion concentration in the electrolytic purification solution is adjusted to 20 to 30 g / L using a sulfuric acid bath, and the electrolytic purification is performed. The method for recovering indium according to any one of claims 1 to 7.
リウム、塩化カリウム等のアルカリ金属塩化物及び塩化
インジウムを使用することを特徴とする請求項８に記載
するインジウムの回収方法。9. The method for recovering indium according to claim 8, wherein hydrochloric acid or an alkali metal chloride such as sodium chloride or potassium chloride and indium chloride are used as the chlorine ion source.
５ｇ／Ｌに調製することを特徴とする請求項８又は９に
記載するインジウムの回収方法。10. An indium concentration in an electrolytic solution of 45 to 5
The method for recovering indium according to claim 8 or 9, wherein the method is adjusted to 5 g / L.
ことを特徴とする請求項８〜１０のそれぞれに記載する
インジウムの回収方法。11. The method for recovering indium according to claim 8, wherein the electrolysis temperature is adjusted to 25 to 50 ° C.
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|---|---|---|---|
| JP2000256759A JP4549501B2 (en) | 2000-08-28 | 2000-08-28 | Indium recovery method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000256759A JP4549501B2 (en) | 2000-08-28 | 2000-08-28 | Indium recovery method |
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| Publication Number | Publication Date |
|---|---|
| JP2002069544A true JP2002069544A (en) | 2002-03-08 |
| JP4549501B2 JP4549501B2 (en) | 2010-09-22 |
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ID=18745321
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|---|---|---|---|
| JP2000256759A Expired - Lifetime JP4549501B2 (en) | 2000-08-28 | 2000-08-28 | Indium recovery method |
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| Country | Link |
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| JP (1) | JP4549501B2 (en) |
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|---|---|---|---|---|
| WO2006080565A1 (en) * | 2005-01-31 | 2006-08-03 | Dowa Metals & Mining Co., Ltd. | Method for recovering indium |
| WO2007015392A1 (en) * | 2005-08-04 | 2007-02-08 | Kobelco Eco-Solutions Co., Ltd. | Method and apparatus for recovering indium from waste liquid crystal display |
| JP2007270342A (en) * | 2006-03-06 | 2007-10-18 | Kobelco Eco-Solutions Co Ltd | Process for recovery of indium and equipment therefor |
| JP2008056999A (en) * | 2006-08-31 | 2008-03-13 | Mitsubishi Materials Corp | Method for recovering indium |
| JP2008056960A (en) * | 2006-08-30 | 2008-03-13 | Mitsubishi Materials Corp | Method for recovering indium |
| WO2008053618A1 (en) | 2006-10-24 | 2008-05-08 | Nippon Mining & Metals Co., Ltd. | Method for collection of valuable metal from ito scrap |
| WO2008053619A1 (en) | 2006-10-24 | 2008-05-08 | Nippon Mining & Metals Co., Ltd. | Method for collection of valuable metal from ito scrap |
| WO2008053616A1 (en) | 2006-10-24 | 2008-05-08 | Nippon Mining & Metals Co., Ltd. | Method for collection of valuable metal from ito scrap |
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| JP2008208437A (en) * | 2007-02-27 | 2008-09-11 | Mitsubishi Materials Corp | Method of recovering indium |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05156381A (en) * | 1991-12-02 | 1993-06-22 | Sumitomo Metal Mining Co Ltd | Method for recovering raw indium for electrolysis |
| JPH0665658A (en) * | 1992-08-21 | 1994-03-08 | Sumitomo Metal Mining Co Ltd | Method for recovering indium from indium scrap |
| JPH10204673A (en) * | 1997-01-22 | 1998-08-04 | Mitsubishi Materials Corp | Recovering method of indium |
| JP2000128531A (en) * | 1998-10-23 | 2000-05-09 | Asahi Puritekku Kk | Separation of indium |
| JP2000169991A (en) * | 1998-12-04 | 2000-06-20 | Dowa Mining Co Ltd | Recovering method of high purity indium |
-
2000
- 2000-08-28 JP JP2000256759A patent/JP4549501B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05156381A (en) * | 1991-12-02 | 1993-06-22 | Sumitomo Metal Mining Co Ltd | Method for recovering raw indium for electrolysis |
| JPH0665658A (en) * | 1992-08-21 | 1994-03-08 | Sumitomo Metal Mining Co Ltd | Method for recovering indium from indium scrap |
| JPH10204673A (en) * | 1997-01-22 | 1998-08-04 | Mitsubishi Materials Corp | Recovering method of indium |
| JP2000128531A (en) * | 1998-10-23 | 2000-05-09 | Asahi Puritekku Kk | Separation of indium |
| JP2000169991A (en) * | 1998-12-04 | 2000-06-20 | Dowa Mining Co Ltd | Recovering method of high purity indium |
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|---|---|---|---|---|
| WO2006080565A1 (en) * | 2005-01-31 | 2006-08-03 | Dowa Metals & Mining Co., Ltd. | Method for recovering indium |
| WO2007015392A1 (en) * | 2005-08-04 | 2007-02-08 | Kobelco Eco-Solutions Co., Ltd. | Method and apparatus for recovering indium from waste liquid crystal display |
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| JP2007270342A (en) * | 2006-03-06 | 2007-10-18 | Kobelco Eco-Solutions Co Ltd | Process for recovery of indium and equipment therefor |
| JP2008056960A (en) * | 2006-08-30 | 2008-03-13 | Mitsubishi Materials Corp | Method for recovering indium |
| JP2008056999A (en) * | 2006-08-31 | 2008-03-13 | Mitsubishi Materials Corp | Method for recovering indium |
| WO2008053616A1 (en) | 2006-10-24 | 2008-05-08 | Nippon Mining & Metals Co., Ltd. | Method for collection of valuable metal from ito scrap |
| WO2008053618A1 (en) | 2006-10-24 | 2008-05-08 | Nippon Mining & Metals Co., Ltd. | Method for collection of valuable metal from ito scrap |
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| JP2008308342A (en) * | 2007-06-12 | 2008-12-25 | Yokohama Kinzoku Kk | Method for obtaining indium compound from waste containing indium oxide |
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