JP2012072479A - Method for recovering indium and tin - Google Patents
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- JP2012072479A JP2012072479A JP2010230955A JP2010230955A JP2012072479A JP 2012072479 A JP2012072479 A JP 2012072479A JP 2010230955 A JP2010230955 A JP 2010230955A JP 2010230955 A JP2010230955 A JP 2010230955A JP 2012072479 A JP2012072479 A JP 2012072479A
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 57
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002386 leaching Methods 0.000 claims abstract description 15
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 9
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 239000011135 tin Substances 0.000 description 42
- 239000000243 solution Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000746 purification Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000032683 aging Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 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
- 239000013077 target material Substances 0.000 description 1
- 239000010409 thin film Substances 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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- Removal Of Specific Substances (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
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 materials containing indium oxide, particularly indium and tin-containing materials such as indium oxide-tin oxide (hereinafter referred to as ITO) target scrap. It relates to the method of recovery.
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.
ＩＴＯターゲットスクラップ材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。
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、従来酸溶解法、溶媒抽出法、イオン交換法などの湿式精錬技術を組み合わせた方法が用いられている。
例えば、特許文献１（特開平８−９１８３８号）に記載された溶媒抽出法を利用した方法があるが、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。Since high-purity materials are used for the ITO target scrap material and the price is high, indium is generally recovered from such scrap material.
Conventionally, as a method for recovering indium from an indium-containing material such as ITO target scrap, a method combining wet refining techniques such as an acid dissolution method, a solvent extraction method, and an ion exchange method has been used.
For example, there is a method using the solvent extraction method described in Patent Document 1 (Japanese Patent Application Laid-Open No. 8-91838). In this method, ITO target waste is dissolved in nitric acid to form indium nitrate, from which an alkyl ester extraction is performed. Indium ions are extracted with a solvent using an agent, and extraction and back-extraction are repeated by replacing the extractant, so that the process becomes complicated and the processing time is prolonged.
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。
更に、いずれの方法もＩＴＯターゲット屑からインジウムの回収を主眼においているため、有価物である錫は回収されず、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、及び錫を回収する方法を開発することである。
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.
Furthermore, since each method focuses on the recovery of indium from the ITO target scrap, the valuable tin is not recovered and is commissioned as an industrial waste, which requires cost.
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.
本発明は、インジウム、スズを含有する物質から高品位のインジウム、すずを容易に回収することを課題とする。 An object of the present invention is to easily recover high-quality indium and tin from a substance containing indium and tin.
本発明者等は、上記の課題を解決したものであり、
（１）酸化インジウム、酸化錫を含有物を塩酸で浸出する浸出工程と、
得られた浸出液にアルカリを加えて、ｐＨ＝１４以上になるように調整し、インジウムは水酸化物として析出させて回収し、錫はアルカリ中和後液として粗分離する工程と、
水酸化インジウムを塩酸浸出した後、インジウム板置換にて錫浄液を行う工程と、から成る高純度のインジウム、及び高純度錫の回収方法。
（２）上記（１）において、その後、亜鉛板置換にてインジウムをスポンジとして回収する工程と、
スポンジを脱水後、アノードに鋳造した後、電解精製する電解精製工程と、
を含む高純度のインジウム、及び高純度錫の回収方法。
（３）上記（１）或は（２）の何れかに記載のアルカリ中和後液を中和して水酸化錫を回収し、溶融還元して錫アノードを鋳造して、錫の電解精製する錫電解精製工程から成る高純度のインジウム、及び高純度錫の回収方法。
を提供する。The inventors have solved the above problems,
(1) a leaching step of leaching a material containing indium oxide and tin oxide with hydrochloric acid;
Adding alkali to the obtained leachate and adjusting the pH to be 14 or higher, indium is precipitated and recovered as hydroxide, and tin is roughly separated as a solution after alkali neutralization;
A method for recovering high-purity indium and high-purity tin, comprising a step of leaching indium hydroxide with hydrochloric acid and then performing tin purification by indium plate replacement.
(2) In the above (1), after that, the step of recovering indium as a sponge by zinc plate substitution;
After dehydrating the sponge, casting it on the anode, and then electrolytically purifying it,
A method for recovering high purity indium and high purity tin.
(3) After neutralizing the alkali-neutralized solution according to either (1) or (2) above, the tin hydroxide is recovered, melted and reduced to cast a tin anode, and the electrolytic purification of tin A high-purity indium comprising a tin electrolytic purification process, and a method for recovering high-purity tin.
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）酸化インジウム、酸化錫を含有物から、高純度インジウム、及び錫を回収することができる。
（２）廃ＩＴＯから有価物を、簡易な方法により容易に回収できる。According to the present invention, the following effects can be obtained.
(1) High purity indium and tin can be recovered from the indium oxide and tin oxide containing materials.
(2) Valuables can be easily recovered from waste ITO by a simple method.
本発明にする原料の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−酸化錫が用いられる。
本発明による高純度インジウム及び錫の回収方法の実態の形態では、ＩＴＯターゲット屑などの酸化インジウム及び酸化錫含有する物を粒径５０μｍ以下になるまで粉砕、篩別したものを６ｍｏｌ／Ｌ以上の塩酸溶液に装入して、温度６０℃以上の温度で浸出後、濾過する。このとき、塩酸溶液は好ましくは６〜８ｍｏｌ／Ｌである。塩酸濃度が６ｍｏＬ／Ｌ以下の場合、インジウムの浸出率が低下し、８ｍｏｌ／Ｌを超えると、塩酸、及び次工程の中和処理に要する薬剤コストが高くなる。
次に、浸出液中のインジウムと錫とを粗分離するため、水酸化ナトリウムを加えて、温度６０℃以上にて、インジウムは水酸化インジウムとし、錫はアルカリ溶液に再浸出して、インジウムと錫とを粗分離する。このとき、反応温度を６０℃以下で行うと、水酸化インジウムの濾過性が悪化するため、６０℃以上を維持する必要がある。The material containing indium oxide as a raw material 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 is used. .
In the actual form of the method for recovering high-purity indium and tin according to the present invention, a material containing indium oxide and tin oxide such as ITO target scraps is pulverized and sieved to a particle size of 50 μm or less, and 6 mol / L or more is obtained. It is charged in a hydrochloric acid solution, leached at a temperature of 60 ° C. or higher, and then filtered. At this time, the hydrochloric acid solution is preferably 6 to 8 mol / L. When the hydrochloric acid concentration is 6 mol / L or less, the leaching rate of indium decreases, and when it exceeds 8 mol / L, the cost of hydrochloric acid and chemicals required for neutralization in the next step increase.
Next, in order to roughly separate indium and tin in the leachate, sodium hydroxide is added, and at a temperature of 60 ° C. or higher, indium becomes indium hydroxide, and tin is leached again into an alkaline solution. Are roughly separated. At this time, if the reaction temperature is 60 ° C. or lower, the filterability of indium hydroxide deteriorates, so it is necessary to maintain 60 ° C. or higher.
次に、インジウム濃度が１００ｇ／Ｌ以上になるように、水酸化インジウムを水にリパルプした後、塩酸にて、ｐＨ１以下になるように調整して、インジウム浸出液を得る。その浸出液中の錫濃度は５００〜１０００ｍｇ／Ｌ含有するため、インジウム板を用いて、インジウム浸出液中錫が検出されなくなるまで、置換浄液する。 Next, indium hydroxide is repulped into water so that the indium concentration is 100 g / L or more, and then adjusted to
錫を置換浄液した後液に、亜鉛板を装入して、亜鉛板置換を行って、インジウムをスポンジインジウムとして回収する。スポンジインジウムは洗浄、脱水後、溶融して、インジウムアノードを鋳造する。このインジウムアノードと、カソード板として、例えば、チタン板、またはインジウム板を用いて、アノードに隔膜を付けて、インジウム電解精製を行うことで高純度インジウムを得ることができる。 A zinc plate is inserted into the liquid after the tin replacement liquid, and the zinc plate is replaced to recover indium as sponge indium. Sponge indium is washed, dehydrated and melted to cast an indium anode. For example, a titanium plate or an indium plate is used as the indium anode and the cathode plate, a diaphragm is attached to the anode, and indium electrolytic purification is performed to obtain high purity indium.
上述の０００９段落に記載した、インジウムと粗分離した錫含有のアルカリ溶液に硫酸を添加して中和し、濾過を行い、水酸化錫を得る。この水酸化錫を乾燥後、コークスとともに、９００〜１０００℃にて加熱して、還元溶融後、得た粗錫メタルをアノードに鋳造する。この錫アノードと、カソードとして、例えば、鉄板、ステンレス板、チタン板、又は錫板のいずれかを用いて、電解精製を行うことで、高純度錫を得ることができる。 Sulfuric acid is added to the tin-containing alkaline solution roughly separated from indium as described in the above paragraph 0009 to neutralize and filter to obtain tin hydroxide. After drying this tin hydroxide, it heats at 900-1000 degreeC with coke, and after reduction melting, the obtained rough tin metal is cast to an anode. High purity tin can be obtained by performing electrolytic purification using, for example, an iron plate, a stainless steel plate, a titanium plate, or a tin plate as the tin anode and the cathode.
この錫アノードと、カソード板として、例えば、ステンレス板、チタン板、鉄板、または錫板を用いて、電流密度１０〜１００Ａ／ｍ２、電解液としては、錫濃度２５〜３５ｇ／Ｌ、水酸化ナトリウム濃度８０〜１２０ｇ／Ｌの溶液にて、電解液温度６０〜８０℃の温度にて錫電解精製を行うことで高純度錫を得ることができる。 For example, a stainless steel plate, a titanium plate, an iron plate, or a tin plate is used as the tin anode and the cathode plate, and the current density is 10 to 100 A / m 2. The electrolytic solution is a tin concentration of 25 to 35 g / L, sodium hydroxide. High-purity tin can be obtained by performing tin electrolytic purification in a solution having a concentration of 80 to 120 g / L at an electrolyte temperature of 60 to 80 ° C.
以下、実施例について、説明する。
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。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、固液分離して、インジウム濃度８２ｇ／Ｌ、錫濃度６．８ｇ／Ｌの浸出液６７０Ｌと、未浸出残渣３ｋｇ−ｗｅｔを回収した。Examples will be described below.
After crushing uncrushed ITO target waste, it was pulverized to 50 μm or less to obtain a powder. 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 to obtain an indium concentration of 82 g / L and a tin concentration of 6.8 g / L. L leaching solution 670 L and unleached residue 3 kg-wet were collected.
この浸出液中のインジウムは水酸化インジウムとして回収、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、水酸化インジウム９２ｋｇ−ｗｅｔと、錫濃度４ｇ／Ｌのアルカリ中和濾液１０５０Ｌ回収した。 Indium in the leaching solution was recovered as indium hydroxide, and sodium hydroxide was added to neutralize the alkali within a temperature range of 60 to 80 ° C. until 90% or more of the tin was leached again into the solution. Thereafter, filtration was performed, and 1050 L of indium hydroxide 92 kg-wet and an alkali neutralized filtrate having a tin concentration of 4 g / L were recovered.
次に、水４００Ｌに水酸化インジウム９２ｋｇ−ｗｅｔをリパルプした後、塩酸を１５０Ｌ添加して、インジウム濃度が１０１ｇ／Ｌ、錫９８０ｍｇ／Ｌの溶液を５５０Ｌ回収した。この溶液にインジウム板を装入して、液中の錫濃度が検出下限以下になるまで、インジウム板置換を行った。
その後、インジウム板を引揚げて、亜鉛板置換を行い、スポンジインジウム５５ｋｇ回収し、洗浄、脱水後、３５０〜４００℃の温度範囲にて溶解後、インジウムアノードを鋳造した。Next, after repulping 92 kg-wet of indium hydroxide into 400 L of water, 150 L of hydrochloric acid was added, and 550 L of a solution having an indium concentration of 101 g / L and tin of 980 mg / L was recovered. An indium plate was charged into this solution, and the indium plate was replaced until the tin concentration in the solution was below the detection lower limit.
Thereafter, the indium plate was lifted up, the zinc plate was replaced, 55 kg of sponge indium was collected, washed and dehydrated, melted in a temperature range of 350 to 400 ° C., and then an indium anode was cast.
このインジウムアノードに隔膜を取り付けて、Ｔｉ板をカソード板として、インジウム濃度５０ｇ／Ｌ、ｐＨ２、電流密度７５Ａ／ｍ２、電解液温度４０℃にて電解精製した。電解液は硫酸インジウム溶液に塩化ナトリウム９５ｇ／Ｌ添加した。その結果、電着インジウムはＳｎ１８ｍａｓｓｐｐｍの高純度インジウムを回収した。 A diaphragm was attached to the indium anode, and a Ti plate was used as a cathode plate, and electrolytic purification was performed at an indium concentration of 50 g / L, pH 2, a current density of 75 A / m 2, and an electrolyte temperature of 40 ° C. The electrolytic solution was 95 g / L of sodium chloride added to the indium sulfate solution. As a result, the electrodeposited indium recovered Sn18 massppm of high purity indium.
００１５段落記載のアルカリ中和濾液１０５０Ｌに、硫酸を添加してｐＨ９〜６の範囲になるように中和後、洗浄、脱水後、水酸化錫１３．５ｋｇを得た。このスポンジ錫８５０〜１０００℃を溶融後、錫アノードを鋳造した。
この錫アノードに、ステンレス板をカソードとして、錫濃度３０ｇ／Ｌ、水酸化ナトリウム濃度１００ｇ／Ｌ溶液にて、電流密度７０Ａ／ｍ２、電解液温度７０℃にて電解精製した。その結果、Ｉｎ１０ｍａｓｓｐｐｍ、電着錫９９．９５ｍａｓｓ％以上の高純度錫を回収した。To 1050 L of the alkali-neutralized filtrate described in paragraph 0015, sulfuric acid was added to neutralize the pH to be in the range of 9 to 6, washed and dehydrated to obtain 13.5 kg of tin hydroxide. After this sponge tin was melted at 850 to 1000 ° C., a tin anode was cast.
The tin anode was subjected to electrolytic purification using a stainless steel plate as a cathode with a tin concentration of 30 g / L and a sodium hydroxide concentration of 100 g / L at a current density of 70 A / m 2 and an electrolyte temperature of 70 ° C. As a result, high purity tin of In10 massppm and electrodeposited tin of 99.95 mass% or more was recovered.
Claims (3)
得られた浸出液にアルカリを加えて、ｐＨ＝１４以上になるように調整し、インジウムは水酸化物として析出させて回収し、錫はアルカリ中和後液として粗分離する工程と、
水酸化インジウムを塩酸浸出した後、インジウム板置換にて錫浄液を行う工程と、から成ることを特徴とする高純度のインジウム、及び高純度錫の回収方法。A leaching step of leaching a material containing indium oxide and tin oxide with hydrochloric acid;
Adding alkali to the obtained leachate and adjusting the pH to be 14 or higher, indium is precipitated and recovered as hydroxide, and tin is roughly separated as a solution after alkali neutralization;
A method for recovering high-purity indium and high-purity tin, comprising: a step of leaching indium hydroxide with hydrochloric acid, and performing a tin cleaning solution by indium plate replacement.
スポンジを脱水後、アノードに鋳造した後、電解精製する電解精製工程と、
を含むことを特徴とする高純度のインジウム、及び高純度錫の回収方法。In claim 1, after that, the step of recovering indium as a sponge by zinc plate replacement;
After dehydrating the sponge, casting it on the anode, and then electrolytically purifying it,
A method for recovering high-purity indium and high-purity tin, comprising:
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| JP2012072483A (en) * | 2010-09-29 | 2012-04-12 | Jx Nippon Mining & Metals Corp | METHOD FOR RECOVERING In AND Sn |
| CN110408958A (en) * | 2019-08-28 | 2019-11-05 | 广东先导稀材股份有限公司 | Method for separating and recovering tin and indium from indium-tin alloy |
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| JP2008240090A (en) * | 2007-03-28 | 2008-10-09 | Dowa Metals & Mining Co Ltd | Indium recovery method |
| JP2009035808A (en) * | 2007-07-12 | 2009-02-19 | Mitsubishi Materials Corp | Method for separating tin from coexistence metal |
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| JPH0967699A (en) * | 1995-08-28 | 1997-03-11 | Kawasaki Steel Corp | Equipment for producing electrotinned steel sheet by halogen process |
| JP2008240090A (en) * | 2007-03-28 | 2008-10-09 | Dowa Metals & Mining Co Ltd | Indium recovery method |
| JP2009035808A (en) * | 2007-07-12 | 2009-02-19 | Mitsubishi Materials Corp | Method for separating tin from coexistence metal |
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| JP2012072483A (en) * | 2010-09-29 | 2012-04-12 | Jx Nippon Mining & Metals Corp | METHOD FOR RECOVERING In AND Sn |
| CN110408958A (en) * | 2019-08-28 | 2019-11-05 | 广东先导稀材股份有限公司 | Method for separating and recovering tin and indium from indium-tin alloy |
| CN110408958B (en) * | 2019-08-28 | 2021-08-13 | 广东先导稀材股份有限公司 | Method for separating and recovering tin and indium from indium-tin alloy |
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