WO2003097903A1 - Procede et dispositif de production de metal hautement pur - Google Patents

Procede et dispositif de production de metal hautement pur Download PDF

Info

Publication number
WO2003097903A1
WO2003097903A1 PCT/JP2003/001113 JP0301113W WO03097903A1 WO 2003097903 A1 WO2003097903 A1 WO 2003097903A1 JP 0301113 W JP0301113 W JP 0301113W WO 03097903 A1 WO03097903 A1 WO 03097903A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
purity
solvent extraction
purity metal
impurities
Prior art date
Application number
PCT/JP2003/001113
Other languages
English (en)
Japanese (ja)
Inventor
Yuichiro Shindo
Kouichi Takemoto
Original Assignee
Nikko Materials Company, Limited
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 Nikko Materials Company, Limited filed Critical Nikko Materials Company, Limited
Publication of WO2003097903A1 publication Critical patent/WO2003097903A1/fr

Links

Classifications

    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/06—Refining
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • 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

Definitions

  • the present invention relates to a method and an apparatus for producing a high-purity metal by electrolytic extraction, which can dissolve and extract a raw material metal using a single electrolytic cell.
  • high-purity metals such as nickel, cobalt, iron, indium, and copper are required to reduce alkali metals, radioactive elements, transition metal elements, and gas components as much as possible. It is widely used, especially as a sputtering target material, for forming compound semiconductors or magnetic thin films.
  • Alkali metals such as Na and K easily move in the gate insulating film and cause deterioration of the MOS-LSI interface characteristics.
  • Radioactive elements such as U and Th cause the soft error of the device due to the emitted ⁇ -rays.
  • transition metal elements such as Fe may cause troubles at interface junctions.
  • gas components such as carbon and oxygen are also undesirable because they cause particles to be generated during sputtering.
  • the solution is purified by ion exchange or solvent extraction, and then purified by electrowinning or electrolytic refining.
  • a method of preceding the solvent extraction step has a problem that the step is complicated and requires a special solvent, so that it is not efficient.
  • high-purity metals such as nickel, cobalt, iron, indium, and copper at the 5N level
  • it is considered to be a relatively simple method to produce them by electrolysis using these metal-containing solutions.
  • separation was difficult due to the large amount of other metal elements (mainly iron) contained in the electrolyte, which was not always efficient. Disclosure of the invention
  • the present invention provides a simple method of electrolyzing a metal raw material such as nickel, cobalt, iron, indium, and copper containing a large amount of other metal elements, carbon, oxygen, and the like, using the metal-containing solution.
  • the purpose of the present invention is to provide a technology for efficiently producing a high-purity metal having a purity of 5 N (99.99.99 wt%) or more from the same raw material.
  • the anode and cathode are separated by an anion exchange membrane, and anolyte is extracted intermittently or continuously and introduced into a solvent extraction tank.
  • a method for producing a high-purity metal characterized in that impurities are removed in the solvent extraction tank, and the high-purity metal electrolyte solution after the removal of the impurities is intermittently or continuously introduced into a power source side.
  • the present invention also provides
  • High-purity metal production equipment by electrolysis including an anode basket containing metal raw materials, an anion-exchange membrane separating the anode and the power source, a cathode for depositing high-purity metal, and impurities from the metal solution (anolyte).
  • a solvent extraction tank a device that intermittently or continuously withdraws anolyte and introduces it into the solvent extraction tank, and intermittently or continuously introduces the high-purity metal electrolyte obtained by solvent extraction to the cathode side
  • High-purity metal characterized by comprising a device
  • the apparatus for producing a high-purity metal according to any one of the above items 5 to 7, further comprising an apparatus for circulating a liquid of ananolite and a catholyte.
  • FIG. 1 is a diagram showing an outline of the electrolysis process.
  • a bulk metal material 2 of 4 N level is put into an anode basket 3 to form an anode 5, and a metal similar to the highly purified metal or another metal material is used for a force sword 4.
  • Perform electrolysis Metal raw materials contain many impurities such as metal elements, carbon, oxygen, etc., other than those of high purity.
  • the bath temperature 1 0 to 7 0 C the metal concentration 2 0 ⁇ : L 2 0 gZL, carried out at a current density 0. 1 ⁇ 1 0 AZdm 2.
  • the productivity will be poor, and if it is too high, for example, if it exceeds 10 AZdm 2 , nodules will tend to occur. Therefore, it is usually desirable that the current density be in the range of 0.1 to 10 A / dm 2 .
  • the anode 5 and the force sword 4 are separated by an anion exchange membrane 6, and intermittently or continuously extracted while circulating an anolyte 7.
  • Catholyte is separated from the outer liquid (anolyte) via the anion exchange membrane 6.
  • the extracted anolyte 7 is introduced into a solvent extraction tank 8.
  • the concentration of other metal elements in the electrolyte can be reduced to approximately 1 mg / L or less.
  • the highly purified metal electrolyte is introduced intermittently or continuously into the power source side, and used as catholyte 9 for electrolytic sampling.
  • the highly purified metal electrolyte may be applied to a filter (not shown) such as activated carbon, if necessary.
  • a filter such as activated carbon
  • the activated carbon filter has an effect of removing impurities from an organic solvent or an organic substance derived from an ion exchange membrane.
  • An electrolyte storage tank 9 for temporarily storing a high-purity metal electrolyte from which impurities such as other metal elements have been removed in a solvent extraction tank is provided and circulated.
  • the highly purified metal electrolyte after the solvent extraction is once stored in the electrolyte storage tank 9, and then intermittently or continuously introduced into the power source from there, and used as the catholyte 9. Collect.
  • the current efficiency is 80 to 100%.
  • an electrodeposited metal having a purity of 5 N or more (precipitated on a power source) can be obtained. That is, excluding gas components, it is 4 N (99.99 wt%) or more, depending on the material, it is 5 N (99.999 wt%) or more, and O: 100 wt ppm or less as an impurity (depending on the material). Is 0: 3 O wtppm or less), and each of C, N, S, and H can be set to 10 wtppm or less.
  • the electrodeposited metal obtained by electrolysis can be subjected to vacuum melting such as electron beam melting.
  • vacuum melting alkali metals such as Na and K and other volatile impurities and gas components can be effectively removed. Examples and comparative examples
  • Electrolysis was performed using 1 kg of 3N-level massive nickel raw material as an anode and a 2N-level nickel plate as a power source.
  • Table 1 shows the content of impurities in the raw materials.
  • Nickel raw materials mainly contain large amounts of iron, carbon, oxygen, and the like.
  • Bath temperature 50 ° (:.., Using a sulfuric acid-based electrolyte, pH 2, was carried out at a current density of 2A / dm 2 electrolysis Initially, N i concentration in the anode side is 20 GZL After the electrolysis, N i concentration 100 GZL Extract as
  • the extracted anolyte was introduced into a solvent extraction tank. Further, impurities such as this precipitate were removed using an activated carbon filter. Thus, the concentration of iron in the electrolyte could be reduced to 1 mg / L or less.
  • this solution was intermittently introduced into the power source side, and used as catholyte for electrowinning.
  • the Ni concentration on the force side is 100 gZL, but the Ni concentration after electrolysis is 20 gZL.
  • Electrodeposited nickel (deposited on a force sword) About lkg was obtained. Purity achieved 5N. That is, it was 5N (99.999 wt%) or more, excluding gas components, O: 30 wt ppm or less as impurities, and C, N, S, respectively, could be 10 wt ppm or less.
  • the above results are compared with the raw materials, and w t p p m
  • electrolysis was performed using 1 kg of a 3N-level massive nickel raw material as an anode and a 2N-level nickel plate as a power source.
  • Table 1 shows the content of impurities in the raw materials.
  • the bath temperature was 50 ° (: using a sulfuric acid-based electrolyte, the nickel concentration was 60 g / L, and the current density was 2 AZ dm 2 .
  • Example 1 the raw material iron was 50 wtp pm to 2 wtp pm, oxygen was 200 wtp pm to less than 10 wtp pm, carbon was 50 wt ppm to less than 10 wt ppm, and N 10 wtppm or less, Slw tp pm or less, Na and K could each be less than 0.1 wtppm c
  • C and N were each less than 10 wtp pm
  • S lw tp pm, and Na and K were each less than 0.1 lw tp pm, but iron 50 w tp pm, cobalt 20 w tp pm, oxygen 60 wt pm, and oxygen
  • the purification effect was inferior to that of, and it was particularly difficult to remove iron and cobalt.
  • Example 1 electrolysis was performed using an electrolytic cell as shown in Fig. 1, using 1 kg of 90 wt% pure cobalt scrap raw material as the anode, and using a 2N level cobalt plate as the power source. went.
  • Table 2 shows the impurity contents of the raw materials.
  • the cobalt raw material mainly contained a large amount of tungsten, titanium, iron, carbon, oxygen and the like.
  • Bath temperature 50 ° (: Using a sulfuric acid-based electrolyte, pH 2 and current density 2 A / dm 2. At the beginning of electrolysis, the C 0 concentration on the anode side was 20 g / L. After electrolysis , With a CO concentration of 100 g / L.
  • the extracted anolyte was introduced into a solvent extraction tank. Further, impurities such as this precipitate were removed using an activated carbon filter. As described above, the concentration of metal element impurities such as iron and tungsten in the electrolyte could be reduced to 1 mgZL or less. After removal of the impurities, this solution was intermittently introduced to the power source side, and used as a catholyte for electrowinning.
  • the Co concentration on the cathod side was 100 gZL, but the Co concentration after electrolysis was less than 20 g / L.
  • Example 1 electrolysis was performed using an electrolytic cell as shown in FIG. 1, using 1 kg of a 2N-level massive iron raw material as an anode, and using a 2N-level iron plate as a power source.
  • Table 3 shows the content of impurities in the raw materials.
  • Iron raw materials mainly contained large amounts of aluminum, arsenic, boron, cobalt, chromium, nickel, zinc, copper, carbon, oxygen, and the like.
  • the test was performed at a bath temperature of 50 ° C., a sulfuric acid-based electrolyte, and at a pH of 2 and a current density of 2 A / dm 2 .
  • the iron concentration on the anode side is 20 gZL.
  • extract with an iron concentration of 100 g / L was introduced into a solvent extraction tank. Further, impurities such as this precipitate were removed using an activated carbon filter. As described above, the concentration of metal element impurities such as nickel and cobalt in the electrolyte could be reduced to 1 mg / L or less.
  • this solution was intermittently introduced into the power source side, and used as catholyte for electrowinning.
  • the iron concentration on the force sword side was 100 g / L, but the iron concentration after electrolysis was less than 20 gZL each.
  • Electrodeposited iron (precipitated on a force sword) About lkg was obtained. Purity achieved 5 N. That is, except for gas components, the content is 5 N (99.99 wt%) or more, and as impurities, O: 20 w tp pm and C, N, and S can be each set to 10 wt pm or less.
  • Table 3 compares the above results with the raw materials.
  • Example 1 electrolysis was performed using an electrolytic cell as shown in FIG. 1, using 1 kg of indium scrap raw material having a purity of 90 wt% level as an anode, and using a 2 N level indium plate as a power source. went.
  • Table 4 shows the content of impurities in the raw materials.
  • the indium raw material mainly contained a large amount of bismuth, antimony, lead-iron, zinc, silver, copper, aluminum, carbon, oxygen, and the like.
  • the indium concentration on the anode side is 20 gZL ( after electrolysis, the indium concentration is extracted as 100 g / L. 0
  • the extracted anolyte was introduced into the solvent extraction tank. Further, impurities such as this precipitate were removed using an activated carbon filter. From the above, the concentration of metal element impurities in the electrolyte could be reduced to 1 mg / L or less.
  • this solution was intermittently introduced to the power source side, and used as a catholyte for electrowinning.
  • the indium concentration on the kaleid side was 100 gZL
  • the indium concentration after electrolysis was less than 20 gZL each.
  • Electrodeposited indium (deposited on a force sword) was obtained in an amount of about lkg. Purity achieved 4 N. That is, excluding gas components, it was 4 N (9.99.9 wt%) or more, and 0: 20 wt p pm and C, N, and S, respectively, as impurities could be reduced to 10 wt p pm or less. Table 4 compares the above results with the raw materials.
  • Example 4 2 3 ⁇ 1 2 1 ⁇ 1 ⁇ 1 ⁇ 1 w t p pm (other than% display) 4Z2
  • Example 4 20 10 10 10 10 10 (Example 5)
  • Example 1 electrolysis was performed using an electrolytic cell as shown in FIG. 1, using 1 kg of a 4 N-level pure copper raw material as an anode, and using a 2N-level copper plate as a power source.
  • Table 5 shows the content of impurities in the raw materials. Copper raw materials mainly contained large amounts of iron, chromium, nickel, silver, aluminum, antimony, selenium, silicon, sulfur, oxygen, and the like.
  • the test was performed at a bath temperature of 50 ° C and a nitric acid-based electrolyte at a pH of 2 and a current density of 2 A / dm 2 .
  • the copper concentration on the anode side is 20 gZL.
  • the extracted anolyte was introduced into a solvent extraction tank. Further, impurities such as the precipitate were removed using an activated carbon filter. From the above, the concentration of metal element impurities in the electrolyte could be reduced to 1 mgZL or less.
  • this solution was intermittently introduced to the power source side, and used as a catholyte for electrowinning.
  • the copper concentration on the force sword side was 100 g / L, but the copper concentration after electrolysis was less than 20 gZL each.
  • Electrodeposited copper (deposited on force sword) Approximately lkg was obtained. Purity achieved 6N. That is, the content was 6 N (99.9999 wt%) or more, excluding gas components, and as impurities, ⁇ , S: lw tp pm or less, and C, N, S could each be 10 wt ppm or less. Table 5 compares the above results with the raw materials.
  • Example 4 From the above, the anode and the force sword of the present invention were separated by an anion exchange membrane, and the anolyte was extracted intermittently or continuously. Removal of impurities such as elements, and further removal of impurities using a filter, and intermittently or continuously placing the removed liquid on the power source side for electrolytic sampling, remove impurities such as metal elements. It can be seen that this is a simple and very effective method for effectively removing and obtaining high-purity metals. The invention's effect
  • a high-purity metal-containing solution is used as the electrolytic solution, and a metal raw material containing a large amount of other metal elements, non-metals, carbon, oxygen, etc., is used for electrowinning using the metal-containing solution for electrolysis.
  • Purity 4 N (99.99 wt%) or 5 N (99.99 wt%) from the same raw material by improving the simple manufacturing process It has a remarkable effect that the above high-purity metals can be produced efficiently.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

La présente invention concerne un procédé de production de métal hautement pur caractérisé. A cet effet, on procède par électrolyse avec utilisation d'une solution métallique. L'anode est séparée de la cathode par une membrane d'échange d'anions. On prélève en continu ou par intermittence un anolyte à envoyer vers un bac d'extraction au solvant. En outre, on introduit en continu ou par intermittence dans le réservoir d'extraction au solvant, au voisinage de la cathode, un électrolyte métallique hautement pur dont les impuretés, et notamment le fer ont été retirées. L'invention constitue ainsi un procédé simple pour réaliser une électrolyse en partant d'un matériau métallique contenant de grandes quantités de fer, de carbone et d'oxygène par utilisation d'une solution métallique. Ce procédé permet de produire de façon efficace un métal hautement pur d'un indice de pureté d'au moins 4N (99,99 % massique) ou d'au moins 5N (99,999 % massique).
PCT/JP2003/001113 2002-05-21 2003-02-04 Procede et dispositif de production de metal hautement pur WO2003097903A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2002145630 2002-05-21
JP2002-145630 2002-05-21
JP2002323541A JP2004043946A (ja) 2002-05-21 2002-11-07 高純度金属の製造方法及び装置
JP2002-323541 2002-11-07

Publications (1)

Publication Number Publication Date
WO2003097903A1 true WO2003097903A1 (fr) 2003-11-27

Family

ID=29552314

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/001113 WO2003097903A1 (fr) 2002-05-21 2003-02-04 Procede et dispositif de production de metal hautement pur

Country Status (3)

Country Link
JP (1) JP2004043946A (fr)
TW (1) TWI252875B (fr)
WO (1) WO2003097903A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8784639B2 (en) 2008-03-20 2014-07-22 Rio Tinto Fer Et Titane Inc. Electrochemical process for the recovery of metallic iron and chlorine values from iron-rich metal chloride wastes

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1276129C (zh) * 2004-07-28 2006-09-20 金川集团有限公司 一种制备高纯镍的方法
JP4745400B2 (ja) * 2006-10-24 2011-08-10 Ｊｘ日鉱日石金属株式会社 Ｉｔｏスクラップからの有価金属の回収方法
KR101623629B1 (ko) 2011-03-07 2016-05-23 제이엑스 킨조쿠 가부시키가이샤 구리 또는 구리 합금, 본딩 와이어, 구리의 제조 방법, 구리 합금의 제조 방법 및 본딩 와이어의 제조 방법
KR101696161B1 (ko) * 2013-09-27 2017-01-13 제이엑스금속주식회사 고순도 In 및 그 제조 방법
WO2015064201A1 (fr) * 2013-11-01 2015-05-07 Jx日鉱日石金属株式会社 In TRÈS PUR ET SON PROCÉDÉ DE PRODUCTION
JP6448417B2 (ja) * 2014-10-02 2019-01-09 Ｊｘ金属株式会社 高純度錫の製造方法、高純度錫の電解採取装置及び高純度錫
JP6532734B2 (ja) 2015-03-31 2019-06-19 Ｊｘ金属株式会社 タングステンを含む有価物の回収方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115222A (en) * 1976-10-25 1978-09-19 National Research Institute For Metals Method for electrolytic winning of lead
JPS6431988A (en) * 1987-07-29 1989-02-02 Sumitomo Metal Mining Co Method for refining indium
WO1993020262A1 (fr) * 1992-04-01 1993-10-14 Rmg Services Pty. Ltd. Systeme electrochimique pour l'extraction des metaux a partir de leurs composes.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115222A (en) * 1976-10-25 1978-09-19 National Research Institute For Metals Method for electrolytic winning of lead
JPS6431988A (en) * 1987-07-29 1989-02-02 Sumitomo Metal Mining Co Method for refining indium
WO1993020262A1 (fr) * 1992-04-01 1993-10-14 Rmg Services Pty. Ltd. Systeme electrochimique pour l'extraction des metaux a partir de leurs composes.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8784639B2 (en) 2008-03-20 2014-07-22 Rio Tinto Fer Et Titane Inc. Electrochemical process for the recovery of metallic iron and chlorine values from iron-rich metal chloride wastes

Also Published As

Publication number Publication date
TW200307060A (en) 2003-12-01
TWI252875B (en) 2006-04-11
JP2004043946A (ja) 2004-02-12

Similar Documents

Publication Publication Date Title
JP4840808B2 (ja) 高純度ニッケル、高純度ニッケルターゲット及び高純度ニッケル薄膜
TWI628287B (zh) 高純度錫及其製造方法
JP5043028B2 (ja) Ｉｔｏスクラップからの有価金属の回収方法
WO2001090445A1 (fr) Procede de production de metal de purete superieure
US6818119B2 (en) Method for processing metals
JP2013079443A (ja) インジウム又はインジウム合金の回収方法及び装置
JP3825984B2 (ja) 高純度マンガンの製造方法
KR100614891B1 (ko) 고순도 인듐 회수방법
WO2003097903A1 (fr) Procede et dispositif de production de metal hautement pur
JPH10204673A (ja) インジウムの回収方法
JP3825983B2 (ja) 金属の高純度化方法
JPH073486A (ja) 高純度コバルト及びその製造方法
JP3878407B2 (ja) 金属の高純度化方法
JP3878402B2 (ja) 金属の高純度化方法
JPH06192874A (ja) コバルトの精製方法
JP3095730B2 (ja) 高純度コバルトの製造方法
JP2004099975A (ja) ルテニウム及び／又はイリジウムの回収方法
JP3151195B2 (ja) コバルトの精製方法
CN114808036A (zh) 一种从ito靶材废料回收高纯锡铟合金的方法
JP2000204494A (ja) 高純度チタン及びその製造方法
JPH11350179A (ja) 高純度コバルトの製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT SE SI SK TR

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase