JP5587728B2 - In and Sn recovery methods - Google Patents
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- JP5587728B2 JP5587728B2 JP2010233030A JP2010233030A JP5587728B2 JP 5587728 B2 JP5587728 B2 JP 5587728B2 JP 2010233030 A JP2010233030 A JP 2010233030A JP 2010233030 A JP2010233030 A JP 2010233030A JP 5587728 B2 JP5587728 B2 JP 5587728B2
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- 238000000034 method Methods 0.000 title claims description 34
- 229910052718 tin Inorganic materials 0.000 title claims description 33
- 229910052738 indium Inorganic materials 0.000 title claims description 28
- 238000011084 recovery Methods 0.000 title description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000005498 polishing Methods 0.000 claims description 7
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000011135 tin Substances 0.000 description 27
- 239000003513 alkali Substances 0.000 description 8
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 5
- 229910003437 indium oxide Inorganic materials 0.000 description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- AZWHFTKIBIQKCA-UHFFFAOYSA-N [Sn+2]=O.[O-2].[In+3] Chemical compound [Sn+2]=O.[O-2].[In+3] AZWHFTKIBIQKCA-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
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- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、インジウム及び錫の回収方法に関し、特に、酸化インジウムを含有する物質、特に酸化インジウム−酸化錫（以下、ＩＴＯと略称）ターゲットスクラップなどのインジウム及び錫含有塊状物から、金属インジウム及び錫を回収する方法に関する。 The present invention relates to a method for recovering indium and tin, and in particular, metal indium and tin from indium and tin-containing masses such as indium oxide-containing materials, particularly indium oxide-tin oxide (hereinafter referred to as ITO) target scrap. It is related with the method of collect | recovering.
近年の液晶技術の急速な進展により、液晶の透明導電膜やガスセンサー等として使用されるＩＴＯ膜の需要は著しく増加しており、このＩＴＯの膜の製造原料として使用されるＩＴＯターゲット材の需要は増大している。
これに伴い、ＩＴＯ用のスパッタリングターゲットを用いて透明導電性薄膜を製造する際には、ターゲットの消耗は均一に進行するわけではないため、消耗の激しい部分がパッキングプレートに達する前にスパッタリングを停止しなければならない。このため、ターゲット全量を使いきることは出来ず、かなりの部分がスクラップとなる。Due to the rapid development of liquid crystal technology in recent years, the demand for ITO films used as liquid crystal transparent conductive films and gas sensors has increased remarkably, and the demand for ITO target materials used as raw materials for the production of ITO films. Is increasing.
Along with this, when manufacturing a transparent conductive thin film using a sputtering target for ITO, the target consumption does not progress uniformly, so the sputtering is stopped before the heavily consumed part reaches the packing plate. Must. For this reason, the entire amount of the target cannot be used up, and a considerable part becomes scrap.
従来、ＩＴＯターゲットスクラップなどのインジウム含有物からインジウムを回収する方法としては、粉砕後、酸溶解法や溶媒抽出、イオン交換法などの湿式精錬による方法の組み合わせが一般的である。
例えば、ＩＴＯスクラップの研磨粉を塩酸溶液にて洗浄及び粉砕後、硝酸に溶解後、溶解液に硫化水素を通じて、亜鉛、錫、鉛、銅など不純物を硫化して沈殿除去した後、これら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。
更に、他の方法では、特許第４２１０７１５号（特許文献１）のように、導電性のある酸化物スクラップを、極性を周期的に反転して電解して、水酸化物を回収することを記載している。 非常に簡便で原料純度を維持したままの有望な方法である。
また、近年の環境問題にも対応した粉砕を介さない処理としても有効な方法ともなっている。
しかし、生成する金属水酸化物は該金属酸化物と異なり導電性がない。そのため、系内に生成した水酸化物がある一定以上増加すると電解に不具合を生じる問題がある。バッチ処理することで回避できるが、生産性が悪くなる欠点がある。
更に、ＩＴＯの端材をバスケット形状の構造体電極に、追い入れしないといけない。また、ＩＴＯの端材に電流を流すため、電極（Ｐｔ線）が劣化する。更には、上記バスケット電解であるため、電槽内、電極内での電流バラツキが大きい。等の問題があった。
特許文献２では、溶媒抽出法を利用した方法の記載があるが、この方法は、ＩＴＯターゲット屑を硝酸に溶解して硝酸インジウムとし、これからアルキルエステル系抽出剤を用いてインジウムイオンを溶媒抽出し、抽出剤を代えて抽出および逆抽出を繰り返すため工程が煩雑になり、処理時間が長引く欠点がある。
別の方法としては、例えばＩＴＯスクラップの研磨粉を洗浄及び粉砕後、硝酸に溶解し、溶解液に硫化水素を通じて、亜鉛、錫、鉛、銅など不純物を硫化して沈殿除去した後、これら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濾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、粒度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。
また、特許文献３においては、ＩＴＯスクラップ研磨粉を塩酸により溶解後ｐＨを調整し、溶解液中に含まれる錫を水酸化錫として回収する方法があるが、工程が増え設備が大きくなり処理時間が長くなるという欠点がある。
その他にも、上記の方法はいずれも工程が多く、また、操作も複雑であるという問題があった。本発明の目的は、酸化インジウムと酸化錫を含有する物質から容易にかつ高純度のインジウム、及び錫を回収する方法を開発することである。
For example, after polishing and grinding ITO scrap polishing powder with hydrochloric acid solution, dissolving in nitric acid, hydrogen sulfide is passed through the solution, and impurities such as zinc, tin, lead, copper are sulfidized and removed, and then ammonia is added to these. Is neutralized and recovered as indium hydroxide.
Furthermore, in another method, as disclosed in Japanese Patent No. 4210715 (Patent Document 1), a conductive oxide scrap is electrolyzed by periodically reversing the polarity to collect hydroxide. doing. This is a promising method that is very simple and maintains raw material purity.
Moreover, it is also an effective method as a treatment not involving pulverization that can cope with recent environmental problems.
However, unlike the metal oxide, the generated metal hydroxide is not electrically conductive. For this reason, there is a problem that a problem occurs in electrolysis when the amount of hydroxide generated in the system increases beyond a certain level. Although it can be avoided by batch processing, there is a drawback that productivity is deteriorated.
Furthermore, the end material of ITO must be driven into the basket-shaped structure electrode. In addition, since current flows through the ITO end material, the electrode (Pt line) deteriorates. Furthermore, because of the basket electrolysis, there is a large current variation in the battery case and the electrode. There was a problem such as.
In Patent Document 2, there is a description of a method using a solvent extraction method. In this method, ITO target waste is dissolved in nitric acid to form indium nitrate, and then indium ions are solvent extracted using an alkyl ester-based extractant. However, since the extraction and the reverse extraction are repeated by replacing the extractant, there are disadvantages that the process becomes complicated and the processing time is prolonged.
As another method, for example, after cleaning and pulverizing the ITO scrap polishing powder, it is dissolved in nitric acid, hydrogen sulfide is passed through the solution, and impurities such as zinc, tin, lead, copper are sulfided and removed by precipitation. In this method, ammonia is added to neutralize and recover as indium hydroxide. However, indium hydroxide obtained by this method has poor filterability and takes a long time to operate, and there are many impurities such as Si, Al, etc., and indium hydroxide to be produced depends on its neutralization conditions and aging conditions, etc. Since the particle size and the particle size distribution fluctuate, there is a problem that the characteristics of the ITO target cannot be stably maintained when the ITO target is manufactured thereafter.
In Patent Document 3, there is a method of adjusting the pH after dissolving the ITO scrap polishing powder with hydrochloric acid and recovering tin contained in the solution as tin hydroxide. Has the disadvantage of becoming longer.
In addition, each of the above methods has many problems and complicated operations. An object of the present invention is to develop a method for easily recovering high-purity indium and tin from a substance containing indium oxide and tin oxide.
しかし、この方法の場合、ＩＴＯターゲットスクラップを粉砕する工程や粉状物を取り扱うため、作業環境が悪く、吸引すると人体に悪影響を及ぼす。また、粉状物を取り扱うことによって得られた水酸化インジウムはろ過性が悪く、操作に時間を要し、Ｓｉ、Ａｌ等の不純物が多く、又、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、粒度分布等が変動するため、その後、ＩＴＯを製造する際にＩＴＯの特性を完全に均一化できないという問題があった。更に、ＩＴＯ中に含有する錫は回収されず、産業廃棄物として委託処理するため、コストを要していた。その他にも、上記の方法はいずれも工程が多く、また、操作も複雑であるという問題があった。本発明の目的は、酸化インジウムと酸化錫を含有する物質から容易にかつ高純度のインジウム、及び粗錫を回収する方法を開発することである。 However, in the case of this method, since the ITO target scrap is pulverized and a powdery material is handled, the working environment is bad, and if it is sucked, the human body is adversely affected. Further, indium hydroxide obtained by handling the powdery substance has poor filterability and requires time for operation, and there are many impurities such as Si, Al, etc. In addition, the indium hydroxide to be produced has its neutralization conditions and Since the particle size, particle size distribution, etc. fluctuate depending on the aging conditions and the like, there has been a problem that the properties of ITO cannot be completely uniformed when manufacturing ITO thereafter. Furthermore, since the tin contained in the ITO is not recovered and is consigned as industrial waste, costs are required. In addition, each of the above methods has many problems and complicated operations. An object of the present invention is to develop a method for easily recovering high purity indium and crude tin from a material containing indium oxide and tin oxide.
本発明者等は、上記の課題を解決したものであり、
（１）ＩＴＯスクラップ研磨粉を塩酸で溶解し、インジウムとスズの大部分をろ液に溶解し、該溶液をろ過し、
その後、苛性ソーダ濃度２〜３ｍｏｌ／Ｌになるよう苛性ソーダを添加し、Ｉｎを水酸化Ｉｎとして中和することにより、前記浸出液をｐＨ１４以上とした後のろ過により、Ｉｎを水酸化Ｉｎとして残渣中に回収し、残りのスズを液中に再溶解し、ＩＴＯ中のＩｎとＳｎを分離するＩｎ及びＳｎの回収方法。
（２）上記（１）に記載のＩｎ及びＳｎの回収方法において、水酸化Ｉｎの粒径が、平均１μｍかつ標準偏差が０．２〜０．２５であるＩｎ及びＳｎの回収方法。
（３）上記（１）または（２）に記載のＩｎ及びＳｎの回収方法において、ｐＨ１４以上とした後のろ過にて、水酸化Ｉｎを残渣として回収した後のろ液に、ＩＴＯからのＳｎの多くを含むＩｎ及びＳｎの回収方法。
（４）（１）〜（３）のいずれかに記載のＩｎ及びＳｎの回収方法において、前記苛性ソーダ添加による中和を、液温６０〜８０℃にて行うことを特徴とするＩｎ及びＳｎの回収方法。
を提供する。
The inventors have solved the above problems,
(1) Dissolve ITO scrap polishing powder with hydrochloric acid, dissolve most of indium and tin in the filtrate, filter the solution,
Thereafter, caustic soda is added to a concentration of 2 to 3 mol / L, and by neutralizing In as hydroxide In, the leaching solution is adjusted to pH 14 or higher, and filtration is performed to make In as hydroxide In and into the residue. A method for recovering In and Sn, in which the remaining tin is redissolved in a liquid and In and Sn in ITO are separated.
(2 ) The method for recovering In and Sn according to the above (1 ), wherein the particle size of In hydroxide is 1 μm on average and the standard deviation is 0.2 to 0.25.
( 3 ) In the method for recovering In and Sn as described in (1) or (2) above, the filtrate after recovering In hydroxide as a residue by filtration after adjusting the pH to 14 or higher is added to Sn from ITO. Recovery method for In and Sn containing a large amount of
(4) In the method for recovering In and Sn according to any one of (1) to (3), neutralization by addition of the caustic soda is performed at a liquid temperature of 60 to 80 ° C. Collection method.
I will provide a.
本発明によれば、以下の効果を得ることができる。
（１）容易にＩＴＯ中のＩｎとＳｎが分離できる。
（２）平均粒径が、小さくかつ粒径がそろっている為、水酸化Ｉｎが、ろ過し易くかつ再溶解し易い。According to the present invention, the following effects can be obtained.
(1) In and Sn in ITO can be easily separated.
(2) Since the average particle diameter is small and the particle diameters are uniform, In hydroxide is easy to filter and redissolve easily.
本発明にする原料の酸化インジウムと酸化インジウムを含有する物質として、特に限定するものはないが、例えば、ＩＴＯターゲットスクラップなどのような、酸化錫を７〜２０％程度含んだ酸化インジウム−酸化錫塊状物が用いられる。 The material containing indium oxide and indium oxide as raw materials according to the present invention is not particularly limited. For example, indium oxide-tin oxide containing about 7 to 20% of tin oxide such as ITO target scrap. A lump is used.
次に、未粉砕のＩＴＯターゲット屑を解砕した。解砕には、クラッシァーミル、ボールミル等が使用される。 該粉砕により、溶解可能な粒度に粉砕する。
その粒度は、５０μｍ以下が好ましい。溶解がスムーズになされるからである。Next, unground ITO target scraps were crushed. For crushing, a crusher mill, a ball mill or the like is used. By this pulverization, it is pulverized to a soluble particle size.
The particle size is preferably 50 μm or less. This is because dissolution is performed smoothly.
（塩酸溶解）
粉砕した、この粉末を塩酸により溶解する。 塩酸の濃度は、４から８ｍｏｌ／Ｌである。
Ｉｎ，Ｓｎの溶解が、好ましく出来るからである。 より好ましくは、５．５から６．５ｍｏｌ／Ｌである。 塩酸と上記粉末との割合は、０５から０．２ＩＴＯ粉砕粉ｋｇ／塩酸Ｌである。
粉砕粉を塩酸溶液に投入し、５０から８０℃に加温する。加温後、２から８時間攪拌をしつつ、行う。
溶解が十分された後、ろ過機等により、固液分離する。
ほとんどのインジウム、スズが、溶解された。
残渣中には、未溶解部分が、多少存在した。(Hydrochloric acid dissolution)
The ground powder is dissolved with hydrochloric acid. The concentration of hydrochloric acid is 4 to 8 mol / L.
This is because dissolution of In and Sn can be preferably performed. More preferably, it is 5.5 to 6.5 mol / L. The ratio of hydrochloric acid to the above powder is 05 to 0.2 ITO ground powder kg / hydrochloric acid L.
The ground powder is put into a hydrochloric acid solution and heated to 50 to 80 ° C. After warming, it is carried out with stirring for 2 to 8 hours.
After dissolution is sufficient, solid-liquid separation is performed with a filter or the like.
Most indium and tin were dissolved.
There were some undissolved parts in the residue.
（アルカリ中和）
上記、浸出液をアルカリ中和する。
強アルカリにより、中和するｐＨ＝１４以上である。 アルカリ剤としては、苛性ソーダ、水酸化カルシウム等を使用する。 例えば、苛性ソーダであれば、その濃度は、２〜３ｍｏｌ／Ｌになるようにする。
上記浸出液をろ過し、ろ液と残渣をえる。
この際、液温度は、６０〜８０℃とする。反応を促進するためである。
残渣には、インジウムが、水酸化Ｉｎとして回収される。
ろ液中には、錫は９０％以上が液に再浸出する。
その時の水酸化Ｉｎの平均粒径は、１．０μｍ前後と極めて、細かい粒度であり、ろ過性が極めて良い。(Alkali neutralization)
The leachate is neutralized with alkali.
The pH to be neutralized by strong alkali is 14 or more. As the alkaline agent, caustic soda, calcium hydroxide or the like is used. For example, in the case of caustic soda, the concentration is set to 2 to 3 mol / L.
The leachate is filtered to obtain filtrate and residue.
At this time, the liquid temperature is set to 60 to 80 ° C. This is to promote the reaction.
In the residue, indium is recovered as In hydroxide.
In the filtrate, 90% or more of tin re-leaches into the liquid.
At that time, the average particle diameter of In hydroxide is as fine as about 1.0 μm, and the filterability is very good.
以下、実施例について、説明する。Examples will be described below.
未粉砕のＩＴＯターゲット屑を解砕した後に、粉砕して５０μｍ以下に粉砕して粉末を得た。
（塩酸溶解）
この粉末、７５ｋｇを塩酸６ｍｏｌ／Ｌの溶液７００Ｌに装入して、６０℃に加温して、５時間攪拌した後、固液分離した。
Ｉｎ濃度８２ｇ／Ｌ、Ｓｎ濃度６．８ｇ／Ｌの浸出液６７０Ｌと、未浸出残渣３ｋｇ−ｗｅｔを回収した。
（アルカリ中和）
上記浸出液をアルカリで、ｐＨ＝１４以上で中和した。
この浸出液中のＩｎは、水酸化Ｉｎとして残渣中に回収した。
錫は９０％以上が液に、再浸出するまで、水酸化ナトリウムを添加して６０〜８０℃の温度範囲内でアルカリ中和した。
その後、濾過を行い、水酸化Ｉｎ９２ｋｇ−ｗｅｔの残渣と、Ｓｎ濃度４ｇ／Ｌのアルカリ中和濾液１０５０Ｌ回収した。
その時の水酸化Ｉｎの平均粒径は１．０７２μｍ、標準偏差０．２３８だった。After crushing uncrushed ITO target waste, it was pulverized to 50 μm or less to obtain a powder.
(Hydrochloric acid dissolution)
75 kg of this powder was charged into 700 L of a 6 mol / L hydrochloric acid solution, heated to 60 ° C., stirred for 5 hours, and then solid-liquid separated.
A leachate 670L having an In concentration of 82 g / L and a Sn concentration of 6.8 g / L and an unleached residue of 3 kg-wet were recovered.
(Alkali neutralization)
The leachate was neutralized with alkali at pH = 14 or higher.
In in the leachate was recovered in the residue as Indium hydroxide.
Sodium hydroxide was alkali neutralized within a temperature range of 60 to 80 ° C. until 90% or more of the tin was re-leached into the liquid.
Thereafter, filtration was performed to recover 1050 L of a residue of hydroxylated In92 kg-wet and an alkali neutralized filtrate having an Sn concentration of 4 g / L.
At that time, the average particle diameter of In hydroxide was 1.072 μm, and the standard deviation was 0.238.
（比較例１）
上記浸出液をｐＨ１０．０で中和したところ、アルカリ中和濾液中のＳｎ濃度１９９ｍｇ／Ｌ、水酸化Ｉｎの平均粒径は５．１３８μｍ、標準偏差は０．４２７だった。
粒度が粗く、ろ過性が極めて悪かった。
又、アルカリろ液中のスズが、高く、インジウムとの分離が極めて悪かった。(Comparative Example 1)
When the leachate was neutralized at pH 10.0, the Sn concentration in the alkali neutralized filtrate was 199 mg / L, the average particle size of In hydroxide was 5.138 μm, and the standard deviation was 0.427.
The particle size was coarse and the filterability was extremely poor.
Further, tin in the alkaline filtrate was high, and separation from indium was extremely poor.
Claims (4)
その後、苛性ソーダ濃度２〜３ｍｏｌ／Ｌになるよう苛性ソーダを添加し、Ｉｎを水酸化Ｉｎとして中和することにより、前記浸出液をｐＨ１４以上とした後のろ過により、Ｉｎを水酸化Ｉｎとして残渣中に回収し、残りのスズを液中に再溶解し、ＩＴＯ中のＩｎとＳｎを分離することを特徴とするＩｎ及びＳｎの回収方法。 Dissolve the ITO scrap polishing powder with hydrochloric acid, dissolve most of indium and tin in the filtrate, filter the solution,
Thereafter, caustic soda is added to a concentration of 2 to 3 mol / L, and by neutralizing In as hydroxide In, the leaching solution is adjusted to pH 14 or higher, and filtration is performed to make In as hydroxide In and into the residue. A method for recovering In and Sn, comprising recovering and re-dissolving the remaining tin in the liquid to separate In and Sn in the ITO.
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