JP5554274B2 - Method for recovering In and Sn and method for recovering In and Sn from an ITO recycled material - Google Patents
Method for recovering In and Sn and method for recovering In and Sn from an ITO recycled material Download PDFInfo
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- JP5554274B2 JP5554274B2 JP2011076667A JP2011076667A JP5554274B2 JP 5554274 B2 JP5554274 B2 JP 5554274B2 JP 2011076667 A JP2011076667 A JP 2011076667A JP 2011076667 A JP2011076667 A JP 2011076667A JP 5554274 B2 JP5554274 B2 JP 5554274B2
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/02—Obtaining tin by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
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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
Description
本発明は、ＩｎとＳｎとを含む合金の回収方法に関し、特に、ＩＴＯスクラップ等のＩｎ−Ｓｎ混合物からＩｎとＳｎとを含む合金を回収するためのＩｎとＳｎとを含む合金の回収方法及びＩＴＯリサイクル材の処理方法に関する。 The present invention relates to a method for recovering an alloy containing In and Sn, and more particularly, a method for recovering an alloy containing In and Sn for recovering an alloy containing In and Sn from an In-Sn mixture such as ITO scrap and the like. The present invention relates to a method for treating ITO recycled material.
従来、酸化インジウム・スズ（ＩＴＯ）の薄膜は、透明導電膜として利用されており、主に、ＩＴＯ焼結体をターゲット材としてスパッタ法や蒸着法によって作製されている。ＩＴＯターゲット材の使用率は低く、使用後の大半がスクラップとして回収されている。Ｉｎ等の資源を有効活用するため、回収したＩＴＯスクラップからＩｎおよびＳｎが回収されている。 Conventionally, a thin film of indium tin oxide (ITO) has been used as a transparent conductive film, and is mainly produced by sputtering or vapor deposition using an ITO sintered body as a target material. The usage rate of the ITO target material is low, and most of the used ITO material is collected as scrap. In and Sn are recovered from the recovered ITO scrap in order to effectively use resources such as In.
ＩＴＯスクラップに代表されるＩｎとＳｎとの混合物からＩｎを選択的に分離して回収する方法に関しては、溶媒抽出や酸浸出があり、特に酸浸出は定法で、塩酸、硫酸、硝酸等の無機酸等がよく用いられる。 Regarding the method of selectively separating and recovering In from a mixture of In and Sn typified by ITO scrap, there are solvent extraction and acid leaching, especially acid leaching is a regular method, and inorganic such as hydrochloric acid, sulfuric acid, nitric acid, etc. Acids are often used.
例えば、特開２０００−１６９９９１号公報（特許文献１）では、ＩＴＯを塩酸で溶解し、これにアルカリを加えてｐＨが０．５〜４となるようにして、Ｓｎを水酸化物として除去し、次に硫化水素ガスを吹き込み、銅、鉛等の有害物として除去し、次いでこの溶解液を用いて電解によってＩｎメタルを電解採取している。 For example, in Japanese Unexamined Patent Publication No. 2000-169991 (Patent Document 1), ITO is dissolved with hydrochloric acid, and alkali is added thereto to adjust the pH to 0.5 to 4, thereby removing Sn as a hydroxide. Then, hydrogen sulfide gas is blown in and removed as harmful substances such as copper and lead, and then In metal is electrolyzed by electrolysis using this solution.
しかしながら、特許文献１に開示された技術では、そもそもこの工程の前段階に、酸浸出を可能にするために、微粉化する必要が有る。しかし近年のＩＴＯは高密度化によって、粉砕が非常に困難で、粉塵等環境対策に莫大な費用がかかる。
However, in the technique disclosed in
また、特許文献１に開示された技術では、回収工程内でのコンタミが発生し、精製工程が必須である。精製には酸処理や硫化処理などがあり、それによって鉛、鉄、銅を除去できるが、そのとき、Ｓｎも除去されてしまう。
Moreover, in the technique disclosed in
ＩＴＯスクラップを酸浸出するために、粉砕ではなく還元して金属化する方法もある。例えば、特開平７−１４５４３２号公報（特許文献２）では、ＩＴＯを水素ガスで還元するとの記載がある。 In order to acid leaching ITO scrap, there is also a method of reducing and metallizing instead of crushing. For example, JP-A-7-145432 (Patent Document 2) describes that ITO is reduced with hydrogen gas.
しかしながら、特許文献２に開示された技術では、還元温度が比較的高いため、実際にはＩｎ成分が少なからず揮発してしまう場合がある。また、実施例に示されるように、生成した還元金属中の不純物としてのＦｅ含有率は高い。高純度のＩｎを得ようとすると、電解精製、酸浸出などでＩｎ単独として分離することとなり、ここでもＳｎが除去されることになる。 However, in the technique disclosed in Patent Document 2, since the reduction temperature is relatively high, the In component may actually be volatilized rather than a small amount. Moreover, as shown in the Examples, the Fe content as an impurity in the produced reduced metal is high. If high purity In is to be obtained, it will be separated as In alone by electrolytic purification, acid leaching, etc., and Sn will also be removed here.
上記課題を鑑み、本発明は、原料からのＩｎ又はＳｎの損失を抑制でき、且つＩｎとＳｎの合金を高純度で回収可能なＩｎとＳｎとを含む合金の回収方法及びＩＴＯリサイクル材の処理方法を提供することを課題とする。 In view of the above problems, the present invention can suppress loss of In or Sn from a raw material and can recover an alloy of In and Sn that can recover an alloy of In and Sn with high purity, and treatment of an ITO recycled material It is an object to provide a method.
上記課題を解決するために本発明者が鋭意検討した結果、ＩＴＯスクラップ等に含まれるＩｎとＳｎの混合物を適正な温度で還元処理し、得られた溶湯中のスラグを適量抜き取って鋳造することにより、原料からのＩｎ、Ｓｎの損失を抑制しつつ、高純度のＩｎとＳｎを含む合金が得られることを見出した。 As a result of intensive studies by the inventor in order to solve the above-mentioned problems, the mixture of In and Sn contained in ITO scrap or the like is reduced at an appropriate temperature, and an appropriate amount of slag in the resulting molten metal is extracted and cast. Thus, it was found that an alloy containing high-purity In and Sn can be obtained while suppressing loss of In and Sn from the raw material.
かかる知見を基礎として完成した本発明は一側面において、ＩｎとＳｎを含む混合物を溶解炉において還元ガスにより７５０〜１０００℃において還元する工程と、還元により得られる溶湯からスラグを除去する工程と、スラグ除去後の溶湯を鋳造し、ＩｎとＳｎを含む合金を製造する工程とを含むＩｎとＳｎとを回収する方法である。
The present invention completed on the basis of such knowledge, in one aspect, a step of reducing a mixture containing In and Sn with a reducing gas in a melting furnace at 750 to 1000 ° C., a step of removing slag from the molten metal obtained by reduction, This is a method of recovering In and Sn including casting a molten metal after removing slag and producing an alloy containing In and Sn.
本発明のＩｎとＳｎとを回収する方法は一実施態様において、スラグを溶湯全容量の１〜３ｍａｓｓ％除去する。
In one embodiment of the method for recovering In and Sn according to the present invention, slag is removed by 1 to 3 mass% of the total molten metal volume.
本発明のＩｎとＳｎとを回収する方法は一実施態様において、還元ガスが、ＲＸガスである。
In one embodiment of the method for recovering In and Sn of the present invention, the reducing gas is RX gas.
本発明は別の一側面において、ＩＴＯリサイクル材を溶解炉において還元ガスにより７５０〜１０００℃において還元する工程と、還元により得られる溶湯からスラグを除去する工程と、除去後の溶湯を鋳造し、ＩｎとＳｎを含む合金を製造する工程とを含むＩＴＯリサイクル材からＩｎとＳｎとを回収する方法である。
In another aspect of the present invention, the step of reducing the ITO recycled material with a reducing gas at 750 to 1000 ° C. in a melting furnace, the step of removing slag from the molten metal obtained by reduction, and casting the molten metal after removal, A method for recovering In and Sn from an ITO recycled material including a step of producing an alloy containing In and Sn .
本発明によれば、原料からのＩｎ又はＳｎの損失を抑制でき、ＩｎとＳｎの合金を高純度で回収可能なＩｎとＳｎとを回収する方法及びＩＴＯリサイクル材からＩｎとＳｎとを回収する方法が提供できる。
According to the present invention, it is possible to suppress the In or loss of Sn from the raw material, In, Sn and In, and alloys of the recoverable high purity In a Sn Sn from methods and ITO recycled material to recovered recovered A method can be provided.
本発明の実施の形態に係るＩｎとＳｎとを回収する方法は、（１）ＩｎとＳｎを含む混合物を溶解炉において還元ガスにより７５０〜１０００℃において還元する工程と、（２）還元により得られる溶湯からスラグを除去する工程と、（３）スラグ除去後の溶湯を鋳造し、ＩｎとＳｎを含む合金を製造する工程とを含む。
How to recovered the In and Sn according to the embodiment of the present invention includes the step of reducing at 750 to 1000 ° C. The reducing gas in the melting furnace a mixture comprising (1) In and Sn, (2) by reduction removing the slag from the resulting molten metal, (3) casting a molten metal after deslagging, including the step of producing an alloy containing in and Sn.
本処理方法による還元雰囲気下での還元によって、不純物が除去可能であることが分かった。理由は明確ではないが、ＩｎとＳｎを含む混合物中に含まれるジルコニウム、鉄等の高融点金属化合物は、本発明の還元処理条件では還元されにくいか、もしくは還元されたとしても鋳造時に溶解しないため、スラグとして除去することにより容易に取り除くことができるものと考えられる。一方で、Ｐｂなどの低融点金属化合物は、この還元処理温度で還元揮発され系外に除去されると推定される。以下、処理方法の具体例について説明する。 It was found that impurities can be removed by reduction under a reducing atmosphere by this treatment method. The reason is not clear, but refractory metal compounds such as zirconium and iron contained in the mixture containing In and Sn are not easily reduced under the reduction treatment conditions of the present invention, or are not dissolved during casting even if reduced. Therefore, it can be easily removed by removing as slag. On the other hand, it is estimated that low melting point metal compounds such as Pb are reduced and volatilized at this reduction treatment temperature and removed from the system. Hereinafter, a specific example of the processing method will be described.
本発明の実施の形態に係る処理方法が処理対象とする原料は、使用済ＩＴＯターゲット、ＩＴＯターゲット作製時の端材等のＩＴＯリサイクル材であり、ＩｎとＳｎを含む混合物である。以下に制限されるものではないが、ＩｎとＳｎを含む混合物中には、例えば８０〜６６ｍａｓｓ％のＩｎと、２〜１４ｍａｓｓ％のＳｎとを含んでいる。ＩｎとＳｎを含む混合物はＩｎとＳｎの他にも０．００５〜０．０５ｍａｓｓ％のＰｂ、０．０１〜０．１ｍａｓｓ％のＦｅ、０．００５〜０．０５ｍａｓｓ％のＡｌ、０．００５〜０．０５ｍａｓｓ％のＮａ、０．０１〜０．１ｍａｓｓ％のＺｒ、０．００５〜０．０５ｍａｓｓ％のＣｌ等を含んでいる。ＩｎとＳｎとを含む混合物（ＩＴＯリサイクル材）は、成型体を粉砕することなくそのまま使用処理できるため、粉砕処理の為の粉塵除去対策などを行う必要がなく、より簡便に処理することができ、且つ環境にも優しい。 The raw material to be processed by the processing method according to the embodiment of the present invention is an ITO recycling material such as a used ITO target and an end material at the time of producing the ITO target, and a mixture containing In and Sn. Although not limited to the following, the mixture containing In and Sn contains, for example, 80 to 66 mass% In and 2 to 14 mass% Sn. In addition to In and Sn, the mixture containing In and Sn is 0.005 to 0.05 mass% Pb, 0.01 to 0.1 mass% Fe, 0.005 to 0.05 mass% Al, 0.005. -0.05 mass% Na, 0.01-0.1 mass% Zr, 0.005-0.05 mass% Cl, etc. are contained. The mixture containing In and Sn (ITO recycle material) can be used as it is without crushing the molded body, so there is no need to take dust removal measures for crushing, and it can be processed more easily. And environmentally friendly.
反応装置としては一般的には溶融炉が用いられるが、還元ガスに対して耐食性を有する材質で形成された反応容器であれば特に制限されない。溶融炉中に吹き込む還元ガスとしては、水素、一酸化炭素、ＲＸガスなどが好適に用いられ、中でもＲＸガスを用いることが好ましい。 As a reaction apparatus, a melting furnace is generally used, but there is no particular limitation as long as it is a reaction vessel formed of a material having corrosion resistance against a reducing gas. As the reducing gas blown into the melting furnace, hydrogen, carbon monoxide, RX gas, or the like is preferably used, and RX gas is preferably used among them.
「ＲＸガス」とは、吸熱型変性ガスを意味し、具体的には天然ガスや都市ガス、プロパンガスなどの炭化水素化合物と空気とを混合加熱分解して発生させるガスを指す。ＲＸガスの組成は、使用する炭化水素化合物にも関係するが、例えば、水素３０〜５０ｖｏｌ％、一酸化炭素２０〜３０ｖｏｌ％、窒素２０〜５０ｖｏｌ％含み、製造コスト的に非常に有利なガスである。 The “RX gas” means an endothermic modified gas, and specifically refers to a gas generated by mixing and pyrolyzing a hydrocarbon compound such as natural gas, city gas, and propane gas and air. The composition of the RX gas is related to the hydrocarbon compound used. For example, the gas contains 30 to 50 vol% hydrogen, 20 to 30 vol% carbon monoxide, and 20 to 50 vol% nitrogen, and is a gas that is very advantageous in terms of production cost. is there.
還元反応は、熱分析測定の発熱ピークである５００℃から開始している。但し実用的な反応速度と処理時間を考慮すると、実質的な還元温度は７５０℃から１０００℃とするのが好ましく、より好ましくは７５０℃から９５０℃、更に好ましくは、８００℃から９２０℃である。還元温度を７５０℃以下とすると、反応が遅く、長時間を要するため生産性が悪くなる場合がある。反応温度が１０００℃を超えると、Ｉｎ化合物が揮発する副反応が多くなって回収等の設備に負荷がかかる場合がある。また、反応温度が１０００℃を超えると、還元雰囲気での炉材にも負荷がかかり交換頻度が高くなる。 The reduction reaction starts at 500 ° C., which is an exothermic peak of thermal analysis measurement. However, considering the practical reaction rate and treatment time, the substantial reduction temperature is preferably 750 to 1000 ° C, more preferably 750 to 950 ° C, and still more preferably 800 to 920 ° C. . When the reduction temperature is 750 ° C. or lower, the reaction is slow and a long time is required, so that productivity may be deteriorated. When the reaction temperature exceeds 1000 ° C., the side reaction in which the In compound volatilizes increases, which may impose a load on the equipment such as recovery. In addition, when the reaction temperature exceeds 1000 ° C., the furnace material in the reducing atmosphere is loaded and the exchange frequency is increased.
上記の還元処理によりＩｎとＳｎを含む溶湯が生成される。この溶湯中には、ジルコニウム、鉄、銅等の不純物（高融点金属化合物）がスラグとして含まれているため、溶湯温度を１６０〜２５０℃程度に冷却して溶湯中からスラグを除去する。スラグ除去量は、溶湯全容量の１〜３ｍａｓｓ％除去することが好ましい。１％未満では、不純物除去が不十分で鋳造合金の純度が低くなる場合がある。３％以上では、鋳造合金の純度は高くなるが、歩留まりが悪くなる場合がある。そして、スラグ除去後の溶湯を鋳型に入れてＩｎとＳｎとを含む合金（Ｉｎ−Ｓｎ合金）を製造する。得られた鋳造合金中の不純物は、各成分１０ｐｐｍ以下、合計１００ｐｐｍ以下である。本方法によれば、Ｉｎ−Ｓｎ品位９９．９９ｍａｓｓ（４Ｎ）以上のＩｎ−Ｓｎ合金が得られる。 A molten metal containing In and Sn is generated by the above reduction treatment. Since this molten metal contains impurities (high melting point metal compounds) such as zirconium, iron, and copper as slag, the molten metal temperature is cooled to about 160 to 250 ° C. to remove the slag from the molten metal. The slag removal amount is preferably removed by 1 to 3 mass% of the total molten metal volume. If it is less than 1%, impurity removal may be insufficient and the purity of the cast alloy may be lowered. If it is 3% or more, the purity of the cast alloy is increased, but the yield may be deteriorated. And the molten metal after slag removal is put into a casting_mold | template, and the alloy (In-Sn alloy) containing In and Sn is manufactured. Impurities in the obtained cast alloy are 10 ppm or less for each component, and a total of 100 ppm or less. According to this method, an In—Sn alloy having an In—Sn quality of 99.99 mass (4N) or more can be obtained.
上記のように本発明の実施の形態を記載したが、この開示の一部をなす論述及び図面はこの発明を限定するものであると理解すべきではない。この開示から当業者には様々な代替実施の形態及び運用技術が明らかとなろう。
本発明では、原料として、ＩＴＯ戻りターゲット、ターゲット作製時の端材などのＩＴＯリサイクル材の成型体の処理を例に説明したが、適当量のＩｎとＳｎを含む混合物であれば、上記と同様な処理により処理可能であることは勿論である。また、原料としては、成型体以外にも、必要に応じて粉砕処理したものを使用してもよいし、平研粉などの微粉状になった材料を使用しても構わない。
Although the embodiments of the present invention have been described as described above, it should not be understood that the descriptions and drawings constituting a part of this disclosure limit the present invention. From this disclosure, various alternative embodiments and operational techniques will be apparent to those skilled in the art.
In the present invention, as an example, the processing of a molded body of an ITO recycled material such as an ITO return target and a milling material at the time of target production has been described as an example. However, if it is a mixture containing an appropriate amount of In and Sn, the same as above Of course, it can be processed by simple processing. In addition to the molded body, the raw material may be pulverized if necessary, or a fine powdered material such as flat polishing powder may be used.
以下、本発明の実施例を示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。 EXAMPLES Examples of the present invention will be described below, but these are provided for better understanding of the present invention and are not intended to limit the present invention.
（実施例１）９００℃での溶解還元処理
ＩＴＯのスクラップ端材１ｋｇを黒鉛るつぼに入れて、マッフル炉でガス還元処理を行った。還元ガスは、ＬＮＧと空気から発生させたＲＸガスを理論量の５倍程度で流し、９００℃で１０時間還元処理した。ＩＴＯが還元されてＩｎとＳｎの合金が得られ、ＩｎとＳｎの回収率はほぼ１００％となった。
得られた溶湯中の不溶解物等のスラグを冷却して溶湯全容量の２ｍａｓｓ％除去し、１８０℃でＩｎ−Ｓｎ合金を鋳造した。鋳造合金中の不純物は、Ｐｂが５ｍａｓｓｐｐｍ以下、Ｆｅが２ｍａｓｓｐｐｍ、Ａｌが１ｍａｓｓｐｐｍ、Ｎａが１０ｍａｓｓｐｐｍ以下、Ｚｒが１ｍａｓｓｐｐｍ以下、塩素が１ｍａｓｓｐｐｍ以下となり、合金としての品位が９９．９９ｍａｓｓ％（４Ｎ）以上であった。
Example 1 Dissolution Reduction Treatment at 900 ° C. 1 kg of ITO scrap scrap was placed in a graphite crucible and subjected to gas reduction treatment in a muffle furnace. As the reducing gas, RX gas generated from LNG and air was flowed at about five times the theoretical amount and reduced at 900 ° C. for 10 hours. ITO was reduced to obtain an alloy of In and Sn, and the recovery rate of In and Sn was almost 100%.
The obtained molten slag such as insoluble matter was cooled to remove 2 mass% of the total molten metal volume, and an In—Sn alloy was cast at 180 ° C. Impurities in the cast alloy are: Pb is 5 massppm or less, Fe is 2 massppm, Al is 1 massppm, Na is 10 massppm or less, Zr is 1 massppm or less, chlorine is 1 massppm or less, and the quality as an alloy is 99.99 mass% (4N) or more. there were.
（実施例２）１０００℃での溶解還元処理
ＩＴＯのスクラップ端材１ｋｇを黒鉛るつぼに入れて、マッフル炉でガス還元処理を行った。還元ガスは、ＬＮＧと空気から発生させたＲＸガスを流し、１０００℃で１０時間処理した。ＩＴＯが還元されてＩｎとＳｎの合金が得られ、その回収率はほぼ１００％となった。
得られた溶湯中の不溶解物等のスラグを冷却して溶湯全容量の２ｍａｓｓ％除去し、１８０℃でＩｎ−Ｓｎ合金を鋳造した。鋳造合金中の不純物は、Ｐｂが１ｍａｓｓｐｐｍ以下、Ｆｅが２ｍａｓｓｐｐｍ、Ａｌが１ｍａｓｓｐｐｍ、Ｎａが１０ｍａｓｓｐｐｍ以下、Ｚｒが１ｐｐｍ以下、塩素が１ｍａｓｓｐｐｍ以下となり、合金としての品位が９９．９９ｍａｓｓ％（４Ｎ）以上であった。
(Example 2) Dissolution reduction treatment at 1000 ° C. 1 kg of ITO scrap scrap was placed in a graphite crucible and subjected to gas reduction treatment in a muffle furnace. As the reducing gas, RX gas generated from LNG and air was flowed and treated at 1000 ° C. for 10 hours. ITO was reduced to obtain an alloy of In and Sn, and the recovery rate was almost 100%.
The obtained molten slag such as insoluble matter was cooled to remove 2 mass% of the total molten metal volume, and an In—Sn alloy was cast at 180 ° C. Impurities in the cast alloy include Pb of 1 massppm or less, Fe of 2 massppm, Al of 1 massppm, Na of 10 massppm or less, Zr of 1 ppm or less, and chlorine of 1 massppm or less. there were.
（実施例３）９００℃還元溶解であり、還元ガスが水素である場合
ＩＴＯのスクラップ端材１ｋｇを黒鉛るつぼに入れて、マッフル炉でガス還元処理を行った。還元ガスには水素を使用し、９００℃で５時間処理した。ＩＴＯが還元されてＩｎとＳｎの合金が得られ、その回収率はほぼ１００％となった。
得られた溶湯中の不溶解物等のスラグを溶湯全容量の２ｍａｓｓ％除去し、１８０℃でＩｎ−Ｓｎ合金を鋳造した。鋳造合金中の不純物は、Ｐｂが１ｍａｓｓｐｐｍ以下、Ｆｅが２ｍａｓｓｐｐｍ、Ａｌが１ｍａｓｓｐｐｍ、Ｎａが１０ｍａｓｓｐｐｍ以下、Ｚｒが１ｍａｓｓｐｐｍ以下、塩素が１ｍａｓｓｐｐｍ以下となり、合金としての品位が９９．９９ｍａｓｓ％（４Ｎ）以上であった。
(Example 3) Reduction melting at 900 ° C. and reduction
2 mass% of the total volume of the molten metal was removed from slag such as insoluble matter in the obtained molten metal, and an In—Sn alloy was cast at 180 ° C. Impurities in the cast alloy include Pb of 1 massppm or less, Fe of 2 massppm, Al of 1 massppm, Na of 10 massppm or less, Zr of 1 massppm or less, and chlorine of 1 massppm or less, and the quality as an alloy is 99.99 mass% (4N) or more. there were.
（比較例１）還元溶解が１１００℃の場合
還元処理の温度を１１００℃とした以外、実施例１と同様に処理した。ＩＴＯが還元されてＩｎとＳｎの合金が得られ、その回収率は９０％とＩｎ成分が揮発飛散してしまった。
得られた溶湯中の不溶解物等のスラグを溶湯全容量の２ｍａｓｓ％除去し、１８０℃でＩｎ−Ｓｎ合金を鋳造した。鋳造合金中の不純物は、Ｐｂが５ｍａｓｓｐｐｍ以下、Ｆｅが２ｍａｓｓｐｐｍ、Ａｌが１ｍａｓｓｐｐｍ、Ｎａが１０ｍａｓｓｐｐｍ以下、Ｚｒが１ｍａｓｓｐｐｍ以下、塩素が１ｍａｓｓｐｐｍ以下となった。比較例１において、合金としての品位は９９．９９ｍａｓｓ％（４Ｎ）以上であったが、還元処理工程においてＩｎ成分の損失が生じた。
(Comparative example 1) When reduction | restoration melt | dissolution is 1100 degreeC It processed similarly to Example 1 except the temperature of the reduction process having been 1100 degreeC. ITO was reduced to obtain an alloy of In and Sn. The recovery rate was 90%, and the In component was volatilized and scattered.
2 mass% of the total volume of the molten metal was removed from slag such as insoluble matter in the obtained molten metal, and an In—Sn alloy was cast at 180 ° C. Impurities in the cast alloy were 5 massppm or less for Pb, 2 massppm for Fe, 1 massppm for Al, 10 massppm or less for Na, 1 massppm or less for Zr, and 1 massppm or less for chlorine. In Comparative Example 1, the quality as an alloy was 99.99 mass% (4N) or more, but loss of In component occurred in the reduction treatment step.
（比較例２）スラグ除去を行わない場合
ＩＴＯのスクラップ端材１ｋｇを黒鉛るつぼに入れて、マッフル炉でガス還元処理を行った。還元ガスは、ＬＮＧと空気から発生させたＲＸガスを流し、９００℃で１０時間還元処理した。ＩＴＯが還元されてＩｎとＳｎの合金が得られ、その回収率はほぼ１００％となった。その後、スラグは除去せずに鋳造を行った。鋳造合金中の不純物は、Ｐｂが５ｍａｓｓｐｐｍ以下、Ｆｅが２ｍａｓｓｐｐｍ、Ａｌが１ｐｐｍ、Ｎａが１０ｍａｓｓｐｐｍ以下、Ｚｒが１ｍａｓｓｐｐｍ以下、塩素が１ｍａｓｓｐｐｍ以下となり、合金としての品位が９９ｍａｓｓ％程度だった。
(Comparative example 2) When slag removal is not performed 1 kg of scrap scrap of ITO was put in a graphite crucible and subjected to gas reduction treatment in a muffle furnace. As the reducing gas, RX gas generated from LNG and air was flowed and reduced at 900 ° C. for 10 hours. ITO was reduced to obtain an alloy of In and Sn, and the recovery rate was almost 100%. Thereafter, casting was performed without removing the slag. The impurities in the cast alloy were Pb of 5 massppm or less, Fe of 2 massppm, Al of 1 ppm, Na of 10 massppm or less, Zr of 1 massppm or less, and chlorine of 1 massppm or less, and the quality of the alloy was about 99 mass%.
Claims (4)
還元により得られる溶湯からスラグを除去する工程と、
スラグ除去後の溶湯を鋳造し、ＩｎとＳｎを含む合金を製造する工程と
を含むＩｎとＳｎとを回収する方法。 Reducing a mixture containing In and Sn at a temperature of 750 to 1000 ° C. with a reducing gas in a melting furnace;
Removing slag from the molten metal obtained by reduction;
A method of recovering In and Sn including casting a molten metal after removing slag and producing an alloy containing In and Sn.
還元により得られる溶湯からスラグを除去する工程と、
スラグ除去後の溶湯を鋳造し、ＩｎとＳｎを含む合金を製造する工程と
を含むＩＴＯリサイクル材からＩｎとＳｎとを回収する方法。 Reducing the ITO recycled material at 750 to 1000 ° C. with a reducing gas in a melting furnace;
Removing slag from the molten metal obtained by reduction;
A method of recovering In and Sn from an ITO recycled material including a step of casting a molten metal after removing slag and producing an alloy containing In and Sn .
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