JP6228879B2 - Metal recovery from scrap - Google Patents

Metal recovery from scrap Download PDF

Info

Publication number
JP6228879B2
JP6228879B2 JP2014069585A JP2014069585A JP6228879B2 JP 6228879 B2 JP6228879 B2 JP 6228879B2 JP 2014069585 A JP2014069585 A JP 2014069585A JP 2014069585 A JP2014069585 A JP 2014069585A JP 6228879 B2 JP6228879 B2 JP 6228879B2
Authority
JP
Japan
Prior art keywords
metal
scrap
suspension
electrolysis
transition metal
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.)
Active
Application number
JP2014069585A
Other languages
Japanese (ja)
Other versions
JP2015190028A (en
Inventor
寿文 河村
寿文 河村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JX Nippon Mining and Metals Corp
Original Assignee
JX Nippon Mining and Metals Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by JX Nippon Mining and Metals Corp filed Critical JX Nippon Mining and Metals Corp
Priority to JP2014069585A priority Critical patent/JP6228879B2/en
Publication of JP2015190028A publication Critical patent/JP2015190028A/en
Application granted granted Critical
Publication of JP6228879B2 publication Critical patent/JP6228879B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Landscapes

  • Electrolytic Production Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Description

本発明は、金属または金属酸化物のスクラップから金属を回収する方法に関する。   The present invention relates to a method for recovering metal from metal or metal oxide scrap.

スクラップからの金属回収は、通常、酸アルカリ等での湿式処理が用いられ、さらに湿式処理の中には懸濁電解を用いる手法がある。当該懸濁電解には、通常、アルカリ溶融塩等が用いられている。このような技術として、例えば、特許文献１に、金属酸化物粉末の電解還元による金属の製造方法であって、該金属酸化物粉末を塩化カルシウム等の溶融塩中に懸濁させ陰極表面で還元することを特徴とする製造方法が開示されている（特許文献１の請求項１、実施例等）。また、特許文献１に記載されているように、電解還元を行う温度は、５００℃以上という非常に特殊な高温での電解条件が採用されている（特許文献１の段落００４３等）。   For metal recovery from scrap, wet processing with an acid alkali or the like is usually used, and there is a technique using suspension electrolysis in wet processing. Usually, an alkali molten salt or the like is used for the suspension electrolysis. As such a technique, for example, Patent Document 1 discloses a method for producing a metal by electrolytic reduction of a metal oxide powder, wherein the metal oxide powder is suspended in a molten salt such as calcium chloride and reduced on the cathode surface. The manufacturing method characterized by doing is disclosed (Claim 1, Example, etc. of Patent Document 1). Further, as described in Patent Document 1, a very special high temperature electrolysis condition of 500 ° C. or higher is adopted as the temperature for performing the electrolytic reduction (paragraph 0043 of Patent Document 1).

また、他の懸濁電解法として、電解液中で陰極底板の上に多数の金属粒子を沈めておき、陰極板を振動させることで粒子を撹拌し、この状態で電析を行う方法もある。これによれば、予め沈めておいた粒子にニッケル、銅などの非鉄金属が堆積し、粒子成長する。この粒子を取り出して金属の回収を行う。   As another suspension electrolysis method, there is a method in which a large number of metal particles are submerged on the cathode bottom plate in an electrolytic solution, the particles are stirred by vibrating the cathode plate, and electrodeposition is performed in this state. . According to this, non-ferrous metals such as nickel and copper are deposited on the previously submerged particles, and the particles grow. The particles are taken out and the metal is recovered.

特開２００７−０１６２９３号公報JP 2007-016293 A

ところで、従来の金属回収方法によれば、電解により生成した金属水酸化物や金属酸化物が溶解できずに析出してしまい、安定的に継続して電気分解を行うことが困難であり、およびこのような析出物を浸出するにも電解液中でそれを行うことは困難である。   By the way, according to the conventional metal recovery method, the metal hydroxide or metal oxide generated by electrolysis is deposited without being dissolved, and it is difficult to perform electrolysis stably and continuously, and In order to leach such deposits, it is difficult to do so in the electrolyte.

また、懸濁電解法では、回収対象の金属を含む懸濁物を電解液として用いることから、スラリーを電解することになり、粒子間抵抗の観点から電解反応による析出電流効率が良好であるとはいえず、エネルギー消費を抑えるという観点からも改良の余地はある。   In the suspension electrolysis method, since the suspension containing the metal to be recovered is used as the electrolytic solution, the slurry is electrolyzed, and the deposition current efficiency by the electrolytic reaction is good from the viewpoint of interparticle resistance. However, there is room for improvement from the viewpoint of reducing energy consumption.

そこで、本発明は、スクラップから金属を回収するに際して、安定的に継続して電解を行い、さらにその電解反応に係る析出電流効率が良好である金属の回収方法を提供することを目的とする。   Accordingly, an object of the present invention is to provide a method for recovering a metal that performs stable and continuous electrolysis when recovering a metal from scrap, and has good deposition current efficiency related to the electrolytic reaction.

本発明者は上述の課題について鋭意検討した結果、スクラップを懸濁電解処理する際に、回収対象の金属よりも卑な金属からなる遷移金属化合物を電解液に添加することにより、電解反応が安定して継続し、結果として電解反応による析出に係る電流効率が良好になることを見出して、本発明を完成するに至った。
すなわち、本発明は以下のとおりである。
（１）金属または金属酸化物のスクラップから金属を回収する方法であって、
前記スクラップを懸濁させた懸濁物に、回収対象の金属よりも卑な金属からなる遷移金属化合物を添加して、当該遷移金属化合物が添加された懸濁物を電解液として電解することにより、回収対象の金属を回収することを特徴とするスクラップからの金属回収方法。
（２）前記遷移金属化合物の金属元素が、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｎのいずれかの一種であることを特徴とする（１）に記載の方法。
（３）前記スクラップがＬｉ、Ｎｉ、Ｃｏ、Ｍｎを少なくとも二種類含むリチウムイオン二次電池用正極材であることを特徴とする（１）または（２）に記載の方法。
（４）前記スクラップが破砕されていることを特徴とする（１）〜（３）のいずれかに記載の方法。 As a result of earnestly examining the above-mentioned problems, the present inventor has stabilized the electrolytic reaction by adding a transition metal compound composed of a metal lower than the metal to be collected to the electrolytic solution when the scrap is subjected to suspension electrolytic treatment. As a result, it was found that the current efficiency related to the precipitation by the electrolytic reaction was improved, and the present invention was completed.
That is, the present invention is as follows.
(1) A method of recovering metal from scrap of metal or metal oxide,
By adding a transition metal compound composed of a base metal rather than the metal to be collected to the suspension in which the scrap is suspended, and electrolyzing the suspension to which the transition metal compound is added as an electrolytic solution A method for recovering metal from scrap, comprising recovering a metal to be recovered.
(2) The method according to (1), wherein the metal element of the transition metal compound is any one of Fe, Ni, Co, and Mn.
(3) The method according to (1) or (2), wherein the scrap is a positive electrode material for a lithium ion secondary battery containing at least two types of Li, Ni, Co, and Mn.
(4) The method according to any one of (1) to (3), wherein the scrap is crushed.

本発明によれば、スクラップから金属を回収するに際して、安定的に継続して電解を行うことを可能にし、その結果その電析に係る電流効率が良好となる。   According to the present invention, when recovering metal from scrap, it is possible to perform electrolysis stably and continuously, and as a result, the current efficiency related to the electrodeposition is improved.

一つの側面から、本発明は、スクラップからの回収方法を提供する。
すなわち、本発明は、金属または金属酸化物のスクラップから金属を回収する方法であって、前記スクラップを懸濁させた懸濁物に、回収対象の金属よりも卑な金属からなる遷移金属化合物を添加して、当該遷移金属化合物が添加された懸濁物を電解液として電解することにより、回収対象の金属を回収することを特徴とするスクラップからの金属回収方法である。 From one aspect, the present invention provides a method for recovering from scrap.
That is, the present invention is a method for recovering a metal from a scrap of metal or metal oxide, wherein a transition metal compound comprising a base metal rather than a metal to be recovered is added to a suspension in which the scrap is suspended. It is a method for recovering metal from scrap, wherein the metal to be recovered is recovered by adding and electrolyzing the suspension added with the transition metal compound as an electrolytic solution.

本発明の対象となるスクラップは、金属または金属酸化物を含むものであれば特に限定されないが、Ｌｉ、Ｎｉ、Ｃｏ、Ｍｎを少なくとも二種類含む電子材料、例えば半導体及び電子部品、液晶ディスプレイ、工具コーティング、ガラスコーティング、光ディスク、ハードディスク、太陽電池、リチウムイオン２次電池用正極材や当該正極材等に用いるスパッタリングターゲット材等由来のスクラップが挙げられる。このため、これらの構成材料に含まれている金属（例えば、Ａｇ、Ａｕ、Ｃｏ、Ｃｒ、Ｃｕ、Ｇａ、Ｇｅ、Ｉｎ、Ｍｎ、Ｍｏ、Ｎｉ、Ｐｄ、Ｐｔ、Ｒｈ、Ｒｕ、Ｓｎ、Ｔａ、Ｔｉ、Ｗ、それらの合金、それらの導電性酸化物等）が、本発明に係る回収対象となる金属である。具体的な金属の種類を、各種用途とともに以下に列挙する：
・半導体及び電子部品：Ａｇ，Ａｌ，Ａｕ，ＡｕＡｓ，ＡｕＳｂ，ＡｕＳｉ，ＡｕＳｎ，Ａｌ2Ｏ3，Ｃｒ，Ｃｕ，ＣｕＣｒ，ＣｒＮｉＡｌ，ＣｒＳｉ，ＧｅＳ2，Ｈｆ，Ｉｒ，Ｍｏ，Ｎｉ，ＮｉＶ，ＯｓＲｕ，Ｐｄ，Ｐｔ，ＰｔＮｉ，Ｒｈ，Ｒｕ，Ｓｉ，Ｔａ，ＴａＡｌ，Ｔｉ，ＷＴｉ，ＷＴｉなど
・液晶ディスプレイ：Ａｇ，Ａｇ合金，Ａｌ，ＡｌＮｄ，Ｃｒ，ＩｎＳｎ，ＩＴＯ，Ｍｏ，ＭｏＷ，Ｓｉ，ＳｉＯ2，Ｔａ，Ｔｉ，Ｗ，ＺｎＡｌ，ＺＡＯ（ＺｎＯ＋Ａｌ2Ｏ3）など
・工具コーティング：Ｃｒ，ＣｒＡｌ，Ｔｉ，ＴｉＡｌなど
・ガラスコーティング：Ａｇ，Ａｇ合金，Ａｌ，Ｂｉ，Ｃｒ，ＩｎＳｎ，ＩＴＯ，Ｎｂ，Ｎｂ2Ｏ5，ＮｉＣｒ，Ｓｉ，ＳｉＯ2，Ｓｎ，Ｔａ2Ｏ5，Ｔｉ，Ｗ，ＺＡＯ（ＺｎＯ＋Ａｌ2Ｏ3），Ｚｎなど
・光ディスク：Ａｌ2Ｏ3，Ｃ，Ｃｏ合金，Ｃｒ，Ｆｅ合金，Ｔａ，Ｔｂ合金，Ｔｅ合金，Ｐｔ，Ｐｔ合金など
・ハードディスク：Ａｌ2Ｏ3，Ｃ，ＣｏＣｒ，ＣｏＣｒＴａ，ＣｏＣｒＰｔ，Ｃｒ，Ｃｒ合金，Ｃｒ酸化物，ＭｇＯ，Ｍｏ，ＮｉＡｌ，ＮｉＳｉ，ＳｉＣ，Ｔａ，Ｔａ2Ｏ5，Ｔｉ酸化物，Ｖ，Ｗなど
・太陽電池：Ａｇ，Ａｌ，ＣＩＧ（Ｃｕ＋Ｉｎ＋Ｇａ），ＣｕＧａ，ＩＴＯ，Ｍｏ，Ｎｉ／ＮｉＶ，Ｓｎ，ＺＡＯ（ＺｎＯ＋Ａｌ2Ｏ3）など
・リチウムイオン２次電池用正極材：正極材としてＬｉＣｏＯ2，ＬｉＮｉＯ2，ＬｉＭｎ2Ｏ4，Ｌｉ（ＣｏxＮｉyＭｎz）Ｏ2〔ｘ＋ｙ＋ｚ＝１〕など、金属としてＮｉ，Ｃｏ，Ｍｎなど、合金としてＮｉＣｏなど。 The scrap that is the subject of the present invention is not particularly limited as long as it contains a metal or metal oxide, but an electronic material containing at least two types of Li, Ni, Co, and Mn, such as a semiconductor and an electronic component, a liquid crystal display, a tool, and the like. Examples include scraps derived from coatings, glass coatings, optical disks, hard disks, solar cells, positive electrode materials for lithium ion secondary batteries, sputtering target materials used for the positive electrode materials, and the like. For this reason, metals contained in these constituent materials (for example, Ag, Au, Co, Cr, Cu, Ga, Ge, In, Mn, Mo, Ni, Pd, Pt, Rh, Ru, Sn, Ta, Ti, W, alloys thereof, conductive oxides thereof, and the like) are metals to be collected according to the present invention. Specific metal types are listed below along with various applications:
Semiconductors and electronic components: Ag, Al, Au, AuAs, AuSb, AuSi, AuSn, Al 2 O 3 , Cr, Cu, CuCr, CrNiAl, CrSi, GeS 2 , Hf, Ir, Mo, Ni, NiV, OsRu, Pd, Pt, PtNi, Rh, Ru, Si, Ta, TaAl, Ti, WTi, WTi, etc. Liquid crystal display: Ag, Ag alloy, Al, AlNd, Cr, InSn, ITO, Mo, MoW, Si, SiO 2 , Ta, Ti, W, ZnAl, ZAO (ZnO + Al 2 O 3 ), etc. Tool coating: Cr, CrAl, Ti, TiAl, etc. Glass coating: Ag, Ag alloy, Al, Bi, Cr, InSn, ITO, Nb, Nb 2 O 5, NiCr, Si, SiO 2, Sn, Ta 2 O 5, Ti, W, ZAO (ZnO + Al 2 O 3), Z Etc., the optical disc: Al 2 O 3, C, Co alloy, Cr, Fe alloy, Ta, Tb alloy, Te alloy, Pt, Pt alloys such as hard disk: Al 2 O 3, C, CoCr, CoCrTa, CoCrPt, Cr, Cr alloy, Cr oxide, MgO, Mo, NiAl, NiSi, SiC, Ta, Ta 2 O 5 , Ti oxide, V, W, etc. Solar cells: Ag, Al, CIG (Cu + In + Ga), CuGa, ITO, Mo , Ni / NiV, Sn, ZAO (ZnO + Al 2 O 3) such as lithium-ion secondary battery cathode material: LiCoO 2, LiNiO 2, LiMn 2 O 4 as a cathode material, Li (Co x Ni y Mn z) O 2 [X + y + z = 1] etc., Ni, Co, Mn etc. as metal, NiCo etc. as alloy.

本発明に係る粉状スクラップからの金属の回収方法は、まず、処理対象となる粉状の金属又は粉状の導電性金属酸化物を含有する原料混合物を準備する。当該原料混合物としては、金属又は導電性金属酸化物のスクラップを粉砕した、いわゆるリサイクル材等が挙げられる。   In the method for recovering metal from powdered scrap according to the present invention, first, a raw material mixture containing powdered metal or powdered conductive metal oxide to be treated is prepared. Examples of the raw material mixture include so-called recycled materials obtained by pulverizing scraps of metals or conductive metal oxides.

次に、アノード及びカソード、電解液を備えた電解槽を準備し、電解液に上記粉状の金属又は粉状の導電性金属酸化物を含有する原料混合物を投入して懸濁させて、電解液を攪拌しながら電気分解を行う。電気分解を行うと、電解液中で懸濁している粉状の金属又は粉状の導電性金属酸化物が、カソードから供給された電子により還元されてカソード表面に析出する。次に、カソード表面に析出した金属を回収する。   Next, an anode and a cathode and an electrolytic cell equipped with an electrolytic solution are prepared. The raw material mixture containing the powdered metal or the powdered conductive metal oxide is put into the electrolytic solution to be suspended, and electrolysis is performed. Electrolysis is performed while stirring the liquid. When electrolysis is performed, powdered metal or powdered conductive metal oxide suspended in the electrolyte is reduced by electrons supplied from the cathode and deposited on the cathode surface. Next, the metal deposited on the cathode surface is collected.

また、電解液として用いる懸濁物は、鉱酸でスクラップを懸濁させて得られる。ここで、懸濁に用いる鉱酸は、硫酸、塩酸、硝酸などが挙げられ、中でも硫酸が好ましい。また、酸による懸濁の条件であるが、ｐＨが３よりは小さくならない程度、また温度が７０℃程度であることが好ましい。   The suspension used as the electrolytic solution is obtained by suspending scrap with mineral acid. Here, examples of the mineral acid used for the suspension include sulfuric acid, hydrochloric acid, nitric acid, and sulfuric acid is preferable. Moreover, although it is the conditions of suspension by an acid, it is preferable that the pH is not lower than 3 and the temperature is about 70 ° C.

次に、電解反応に際して添加する、回収対象の金属よりも卑な遷移金属化合物であるが、回収対象となる金属に応じて適宜選択される遷移金属を有するものである。遷移金属として、具体的には、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｎのいずれかから選択される。
例えば、回収対象の金属がＬｉ、Ｎｉ、Ｃｏである場合、これらよりも卑であるＭｎが遷移金属化合物の金属元素として用いることができる。また、遷移金属化合物は、この金属元素の酸化物、硫化物または硫酸塩、カルボン酸塩等の有機酸塩などが挙げられる。 Next, the transition metal compound is lower than the metal to be collected, which is added in the electrolytic reaction, and has a transition metal appropriately selected according to the metal to be collected. Specifically, the transition metal is selected from any of Fe, Ni, Co, and Mn.
For example, when the metals to be collected are Li, Ni, and Co, Mn, which is lower than these, can be used as the metal element of the transition metal compound. Examples of the transition metal compound include oxides, sulfides or sulfates of these metal elements, and organic acid salts such as carboxylates.

回収対象の金属よりも卑な遷移金属を含む遷移金属化合物を添加することにより、安定した電解反応が継続する理由は明らかではないが、以下の理由が考えられる。
回収対象の金属が、電解により水酸化物や酸化物として電解液中に存在するようになる。そこで、添加された遷移金属により、水酸化物や酸化物の金属成分が還元され、還元された金属が電析される。一方で、還元に寄与した遷移金属が電解反応場で還元されることになり、還元された遷移金属が再度金属水酸化物や金属酸化物の還元に寄与することとなる。このようにして、電解反応により回収対象の金属が還元される環境が継続するためと考えられる。 The reason why a stable electrolytic reaction continues by adding a transition metal compound containing a transition metal that is lower than the metal to be recovered is not clear, but the following reasons are conceivable.
The metal to be collected is present in the electrolyte as hydroxide or oxide by electrolysis. Therefore, the added transition metal reduces the metal component of the hydroxide or oxide, and the reduced metal is electrodeposited. On the other hand, the transition metal contributing to the reduction is reduced in the electrolytic reaction field, and the reduced transition metal contributes again to the reduction of the metal hydroxide or metal oxide. Thus, it is considered that the environment in which the metal to be recovered is reduced by the electrolytic reaction continues.

また、遷移金属化合物は、回収対象の金属に対して１〜５０質量％、好ましくは５〜２０質量％の金属を含有する量で添加することが好ましい。この割合で遷移金属化合物を使用することにより、電解液中に生成する金属水酸化物や金属酸化物の中の金属が効率よく還元され、電解反応により析出するようになる。
これにより、従来における課題の一つとなっていた、電解析出に係る電流効率の改善を図ることができ、例えば積算電流値から見積もった電流効率が、８０％以上とすることが可能になる。また、スクラップに含まれる回収対象金属を１００％としたときの回収率に関しては、１００％回収できることが理想ではあるが、１００％に近くなるにつれ、効率が悪くなるため、例えば９５％の回収率になるまで電解を継続させることが好ましい。 Moreover, it is preferable to add a transition metal compound in the quantity containing 1-50 mass% with respect to the metal of collection | recovery object, Preferably 5-20 mass%. By using the transition metal compound at this ratio, the metal hydroxide generated in the electrolytic solution and the metal in the metal oxide are efficiently reduced and deposited by the electrolytic reaction.
Thereby, it is possible to improve the current efficiency related to electrolytic deposition, which has been one of the problems in the past, and for example, the current efficiency estimated from the integrated current value can be 80% or more. Also, regarding the recovery rate when the recovery target metal contained in the scrap is 100%, it is ideal that 100% recovery is possible, but the efficiency decreases as it approaches 100%. For example, the recovery rate is 95%. It is preferable to continue electrolysis until.

これにより、従来において、電解反応時に生じる水酸化物や酸化物となってスクラップから取り切れなかった金属の回収も可能になり、生産性が向上する。また、電解反応の析出に係る電流効率も上がるため、エネルギー効率が上がり、結果としてコストを下げることが可能になる。   As a result, it is possible to recover a metal that has conventionally become a hydroxide or an oxide generated during an electrolytic reaction and cannot be removed from scrap, thereby improving productivity. In addition, since the current efficiency related to the precipitation of the electrolytic reaction is increased, the energy efficiency is increased, and as a result, the cost can be reduced.

以下、本発明の実施例を示すが、本発明は実施例に限定されるものではない。
（実施例１）
Ｌｉ、Ｎｉ、Ｃｏ、Ｍｎの酸化物からなる正極材のスクラップ粉１ｋｇを硫酸水溶液１０Ｌに懸濁させた。その時のｐＨは４であった。続いてその懸濁液に硫酸マンガン２００ｇを添加した。その懸濁液を電解液として、アノードに寸歩安定化電極（ＤＳＥ）、カソードにＴｉを用いて、１５Ａの定電流にて６０℃で懸濁電解を行った。このときの電流密度は５Ａ／ｄｍ2程度であった。３０時間後、カソードの電極表面に、ＮｉとＣｏの合金が４００ｇ析出、Ｌｉは電解液に溶解した。積算電流値から見積もった析出電流効率は８０％だった。 Examples of the present invention will be described below, but the present invention is not limited to the examples.
Example 1
1 kg of positive electrode material scrap powder composed of oxides of Li, Ni, Co, and Mn was suspended in 10 L of sulfuric acid aqueous solution. The pH at that time was 4. Subsequently, 200 g of manganese sulfate was added to the suspension. Suspension electrolysis was performed at 60 ° C. at a constant current of 15 A using the suspension as an electrolytic solution, using a step-stabilized electrode (DSE) for the anode and Ti for the cathode. The current density at this time was about 5 A / dm 2 . After 30 hours, 400 g of an alloy of Ni and Co precipitated on the electrode surface of the cathode, and Li dissolved in the electrolyte. The deposition current efficiency estimated from the integrated current value was 80%.

（実施例２）
添加剤を酸化Ｍｎとする以外、実施例１と同様に懸濁電解を行った。３０時間後、カソードの電極表面に、ＮｉとＣｏの合金が４００ｇ析出、Ｌｉは電解液に溶解した。積算電流値から見積もった析出電流効率は８０％だった。 (Example 2)
Suspension electrolysis was performed in the same manner as in Example 1 except that the additive was Mn oxide. After 30 hours, 400 g of an alloy of Ni and Co precipitated on the electrode surface of the cathode, and Li dissolved in the electrolyte. The deposition current efficiency estimated from the integrated current value was 80%.

（比較例１）
実施例１で、硫酸マンガンを添加しない以外は、同様に懸濁電解した。３０時間後の析出合金は２５０ｇとなった。電流効率が５０％だった。 (Comparative Example 1)
In Example 1, suspension electrolysis was performed in the same manner except that manganese sulfate was not added. The precipitated alloy after 30 hours was 250 g. The current efficiency was 50%.

Claims (3)

金属または金属酸化物のスクラップから金属を回収する方法であって、
前記スクラップを懸濁させた懸濁物に、回収対象の金属よりも卑な金属からなる遷移金属化合物を添加して、当該遷移金属化合物が添加された懸濁物を電解液として電解することにより、回収対象の金属を回収し、
前記遷移金属化合物の金属元素が、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｎのいずれかの一種であることを特徴とするスクラップからの金属回収方法。 A method for recovering metal from scrap of metal or metal oxide,
By adding a transition metal compound composed of a base metal rather than the metal to be collected to the suspension in which the scrap is suspended, and electrolyzing the suspension to which the transition metal compound is added as an electrolytic solution , Collect the metal to be collected ,
A method for recovering metal from scrap, wherein the metal element of the transition metal compound is one of Fe, Ni, Co, and Mn . 前記スクラップがＬｉ、Ｎｉ、Ｃｏ、Ｍｎを少なくとも二種類含むリチウムイオン二次電池用正極材であることを特徴とする請求項１に記載の方法。 The method according to claim 1 , wherein the scrap is a positive electrode material for a lithium ion secondary battery containing at least two types of Li, Ni, Co, and Mn. 前記スクラップが破砕されていることを特徴とする請求項１又は２に記載の方法。 The method according to claim 1 or 2 , wherein the scrap is crushed.
JP2014069585A 2014-03-28 2014-03-28 Metal recovery from scrap Active JP6228879B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014069585A JP6228879B2 (en) 2014-03-28 2014-03-28 Metal recovery from scrap

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2014069585A JP6228879B2 (en) 2014-03-28 2014-03-28 Metal recovery from scrap

Related Child Applications (1)

Application Number Title Priority Date Filing Date
JP2017187028A Division JP2018003164A (en) 2017-09-27 2017-09-27 Metal recovery method from scrap

Publications (2)

Publication Number Publication Date
JP2015190028A JP2015190028A (en) 2015-11-02
JP6228879B2 true JP6228879B2 (en) 2017-11-08

Family

ID=54424793

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2014069585A Active JP6228879B2 (en) 2014-03-28 2014-03-28 Metal recovery from scrap

Country Status (1)

Country Link
JP (1) JP6228879B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114540623B (en) * 2022-01-28 2023-11-21 佛山汇真科技有限公司 Intelligent rare noble metal separation and purification system and method

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2520674B2 (en) * 1987-12-17 1996-07-31 神岡鉱業株式会社 Method and device for recovering metal supported on carrier
JPH04318185A (en) * 1991-04-15 1992-11-09 Fuji Photo Film Co Ltd Desilverizing method

Also Published As

Publication number Publication date
JP2015190028A (en) 2015-11-02

Similar Documents

Publication Publication Date Title
JP6271964B2 (en) Method for recovering metal from cathode material for lithium ion battery
JP6243614B2 (en) Method for recovering metal from powdered scrap
TWI432609B (en) Method for recovering valuable metal from indium - zinc oxide waste
US8734633B2 (en) Method of recovering valuable metal from scrap containing conductive oxide
US8685225B2 (en) Method of recovering valuable metal from scrap conductive oxide
JP4745400B2 (en) Recovery method of valuable metals from ITO scrap
TWI406954B (en) Method for recovering valuable metals from IZO waste
CN101886178B (en) Comprehensive recovery method for nickel-hydrogen waste battery
CA2831273C (en) Anode for electrowinning and method for electrowinning using same
EP2287364B1 (en) Method for electrolytic winning of zinc
TW200938638A (en) Process for recovery of valuable metals from scrap IZO
TW202106929A (en) Methods for extracting lithium from spodumene
JP4516617B2 (en) Anode for electrowinning zinc and electrowinning method
CN105350028A (en) Nitinol powder prepared through molten salt electrolysis and preparing method of nitinol powder
JP6228879B2 (en) Metal recovery from scrap
JP6100525B2 (en) Method for recovering metal or alloy from scrap of high purity metal or alloy
KR102211986B1 (en) Method for recovering metal from scrap
JP2011208216A (en) Method of recovering indium and tin
CN108163873A (en) A kind of method that lithium hydroxide is extracted in the lithium waste residue from phosphoric acid
JP2018003164A (en) Metal recovery method from scrap
JP6419282B2 (en) Method for recovering metal from powdered scrap
CN106574384B (en) The method for manufacturing titanium using strike
JP5471735B2 (en) Method for removing tin and thallium and method for purifying indium
JP6222067B2 (en) Method for regenerating anode, method for producing indium hydroxide powder, method for producing indium oxide powder, and method for producing sputtering target
JP6816076B2 (en) How to make electrolytic copper

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20160930

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20170522

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20170530

A601 Written request for extension of time

Free format text: JAPANESE INTERMEDIATE CODE: A601

Effective date: 20170726

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20170927

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20171010

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20171016

R150 Certificate of patent or registration of utility model

Ref document number: 6228879

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250