EP4384657B1 - Procédé de production électrolytique de poudre métallique - Google Patents

Procédé de production électrolytique de poudre métallique

Info

Publication number
EP4384657B1
EP4384657B1 EP22760941.9A EP22760941A EP4384657B1 EP 4384657 B1 EP4384657 B1 EP 4384657B1 EP 22760941 A EP22760941 A EP 22760941A EP 4384657 B1 EP4384657 B1 EP 4384657B1
Authority
EP
European Patent Office
Prior art keywords
acid
electrolyte solution
silver
metal
sulfonic acid
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
EP22760941.9A
Other languages
German (de)
English (en)
Other versions
EP4384657A1 (fr
EP4384657C0 (fr
Inventor
Si Jun ZHU
Jin Bo SONG
Jing Cheng XIA
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP4384657A1 publication Critical patent/EP4384657A1/fr
Application granted granted Critical
Publication of EP4384657B1 publication Critical patent/EP4384657B1/fr
Publication of EP4384657C0 publication Critical patent/EP4384657C0/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • 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
    • C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • C25C7/08—Separating of deposited metals from the cathode

Definitions

  • the present invention relates to a process for electrolytic production of metal powder.
  • Fine metal powders such as copper powder and silver powder are widely used in various applications, for example in electronic pastes, lubricants, catalysts, medicines and biofilters. Electrolytic deposition of metal powders has always been an important industrial process, as the process can provide metal powders with high quality under mild conditions and does not impose high requirements of starting materials.
  • US 6,183,545 describes an aqueous solution for the reductive deposition of metals comprising, besides water, (A) a special phosphine, and (B) a soluble compound of a metal or a compound of a metal solubilized through the formation of a soluble complex by said phosphine.
  • JP 2003-342775 relates to a method for producing silver powder, comprising the steps of: performing electrolysis using a silver plate as an anode in an acidic aqueous solution containing at least an alkyl group and a sulfo group and containing trivalent titanium ions; and generating silver powder by causing an oxidation-reduction reaction between the silver ions eluted from the silver plate and the trivalent titanium ions.
  • WO 2015/095664 relates to systems and methods for the recovery of noble metal from noble-metal-containing material, in which an electric current is transported between an electrode and the noble metal of a noble-metal-containing material to dissolve at least a portion of the noble metal from the noble-metal-containing material. The dissolved noble metal can subsequently be precipitated out of solution and recovered.
  • an aqueous copper sulfate solution comprising sulfuric acid was generally adopted.
  • the process needs certain measures for protection against corrosive sulfuric acid release from the electrolyte solution into ambient, particularly under an elevated process temperature.
  • an aqueous silver nitrate electrolyte solution comprising nitric acid was generally adopted.
  • the process also has the problem of nitric acid release from the electrolyte solution into ambient under elevated process temperature.
  • the deposition of silver particles on the cathode is accompanied with quick growth of dendritic aggregates, especially at the corner of the cathode, in the conventional processes using a silver nitrate electrolyte solution.
  • the dendritic aggregates may extend to anode and thus increase the risk of short circuit.
  • a further object of the present invention is to provide a process for production of copper powder or silver powder with desirable or even smaller particle size.
  • the present invention provides a process for production of a powder of metal in an electrolytic cell comprising an anode made of the metal, a cathode and an electrolyte solution, which comprises
  • the present specification also describes the copper or silver powder obtained or obtainable by the process as described herein.
  • aqueous means that an electrolyte solution comprises a solvent containing at least 50% water. Preferably, at least 75%, more preferably 90% of the solvent is water. It can be contemplated that the solvent of the electrolyte solution consists essentially of water without any intentionally added organic solvent. Any type of water may be used, with preference to distilled or deionized water.
  • the present invention provides a process for production of a powder of metal in an electrolytic cell comprising an anode made of the metal, a cathode and an electrolyte solution, which comprises
  • the anode is made of the metal to be deposited on cathode and thus supplies metal ions into the electrolyte solution continuously during the operation of the electrolytic cell.
  • the anode may be made of the metal having a purity of at least 95%, for example at least 98% or at least 99%.
  • the anode is made of copper or silver having a purity within above ranges.
  • cathode there is no particular restriction to the material of cathode.
  • the cathode useful for the process according to the present invention may be made of, for example, stainless steel or titanium.
  • the anode and the cathode may be arranged at a distance of 1 cm to 10 cm, preferably 3 cm to 6 cm, for example 3 cm to 5.5 cm.
  • the electrolyte solution comprising (i) an alkane sulfonic acid or alkanol sulfonic acid and (ii) a soluble metal salt of an alkane sulfonic acid or alkanol sulfonic acid is effective for producing silver and copper powders under an elevated electrolysis temperature, without the problem of acid release into ambient.
  • Useful alkane sulfonic acids as the component (i) may be C 1 -C 12 -alkane sulfonic acids, preferably C 1 -C 6 -alkane sulfonic acids.
  • the alkane sulfonic acids may be monosulfonic acids and disulfonic acids.
  • alkane monosulfonic acids include, but are not limited to methanesulfonic acid, 1-ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid, 1-pentanesulfonic acid, 1-hexanesulfonic acid, 1-decanesulfonic acid and 1-dodecanesulfonic acid.
  • alkane disulfonic acids include, but are not limited to methanedisulfonic acid, 1,1-ethanedisulfonic acid, 1,2-ethanedisulfonic acid, 1,1-propanedisulfonic acid, 1,3-propanedisulfonic acid, 1,1-butanedisulfonic acid and 1,4-butanedisulfonic acid.
  • One alkane sulfonic acid or any mixture of two or more alkane sulfonic acids may be used in the electrolyte solution in the process according to the invention.
  • Useful alkanol sulfonic acids as the component (i) may be C 2 -C 12 -alkanol sulfonic acids, preferably C 2 -C 6 -alkanol sulfonic acids, i.e., hydroxy substituted C 2 -C 12 -, preferably C 2 -C 6 -alkane sulfonic acids.
  • the hydroxy may be on a terminal or internal carbon of alkyl chain of the alkane sulfonic acids.
  • alkanol sulfonic acids include, but are not limited to 2-hydroxy-1-ethanesulfonic acid, 1-hydroxy-2-propanesulfonic acid, 2-hydroxy-1-propanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, 2-hydroxy-1-butanesulfonic acid, 4-hydroxy-1-butanesulfonic acid, 4-hydroxy-2-butanesulfonic acid, 2-hydroxy-1-pentanesulfonic acid, 4-hydroxy-1-pentanesulfonic acid, 2-hydroxy-1-hexanesulfonic acid, 2-hydroxy-1-decanesulfonic acid and 2-hydroxy-1-dodecanesulfonic acid.
  • One alkanol sulfonic acid or any mixture of two or more alkanol sulfonic acids may be used in the electrolyte solution in the process according to the invention.
  • alkane sulfonic acids and alkanol sulfonic acids may be those prepared by any methods known in the art or commercially available ones without particular restrictions.
  • the alkane sulfonic acid or alkanol sulfonic acid as the component (i) may be comprised in the electrolyte solution at a concentration in a range of 1 to 200 grams per liter (g/L) of the electrolyte solution, particularly 5 to 180 g/L, preferably 10 to 150 g/L.
  • the soluble metal salt of an alkane sulfonic acid or alkanol sulfonic acid as the component (ii) refers to a soluble silver or copper salt of alkane sulfonic acid or alkanol sulfonic acid.
  • the soluble silver or copper salt of alkane sulfonic acid or alkanol sulfonic acid will also be referred to as soluble metal sulfonate hereinbelow.
  • the alkane sulfonic acid or alkanol sulfonic acid from which the soluble metal sulfonate is derived may be same as or different from the alkane sulfonic acid or alkanol sulfonic acid as the component (i), and selected from those as described hereinabove for the component (i).
  • the soluble metal sulfonate is a soluble silver or copper salt of the alkane sulfonic acid or alkanol sulfonic acid as the component (i).
  • the soluble metal sulfonate as the component (ii) may be comprised in the electrolyte solution at a concentration in a range of 1 to 200 g/L of the electrolyte solution, particularly 5 to 150 g/L, preferably 5 to 120 g/L, calculated as the metal ions.
  • the electrolyte solution may optionally comprise one or more additives known useful in the art, for example, gelatins derived from collagen (e.g., animal glue), glucose, urea. Some inorganic additives may also be mentioned, for example cupric chloride to improve the electrical conductivity or adjust the pH of the electrolyte solution in the copper powder production.
  • the additives if present, may be comprised in the electrolyte solution at concentration of up to 20 g/L, more preferably up to 10 g/L.
  • the present invention provides a process for production of silver powder in an electrolytic cell comprising an anode made of silver, a cathode and an electrolyte solution, wherein the electrolyte solution comprises (i) an alkane sulfonic acid or alkanol sulfonic acid and (ii) a soluble silver alkane sulfonate or alkanol sulfonate.
  • the soluble silver alkane sulfonate or alkanol sulfonate as the component (ii) is preferably comprised in the electrolyte solution at a concentration in a range of 50 to 200 g/L of the electrolyte solution, particularly 60 to 150 g/L, preferably 80 to 120 g/L, calculated as silver ions.
  • the alkane sulfonic acid or alkanol sulfonic acid as the component (i) is preferably comprised in the electrolyte solution at a concentration in a range of 50 to 200 grams per liter (g/L) of the electrolyte solution, particularly 80 to 200 g/L, preferably 100 to 160 g/L.
  • the process may be carried out at a temperature in the range of 20 °C to 70 °C, preferably 30 °C to 60 °C, more preferably 40 to 50 °C.
  • the metal particles may be removed from the cathode into the electrolyte solution by any mechanical means as well known in the art without any restriction.
  • step c) the electrolyte solution comprising the metal particles as obtained from step b) are subjected to an isolation to provide the metal powder.
  • the isolated meal powder may further be subjected to a post treatment including washing, drying and/or anti-oxidation treatment.
  • the post treatment may be carried out with any conventional means.
  • the isolated meal powder may be washed with deionized water, dried under vacuum and reduced under an atmosphere of hydrogen.
  • process according to the present invention may further comprises following steps:
  • the present invention provides a process for production of a silver powder in an electrolytic cell comprising an anode made of silver, a cathode and an electrolyte solution, which comprises
  • the electrolyte solution comprises (i) a C 1 -C 6 -alkane sulfonic acid or alkanol sulfonic acid at a concentration in a range of 1 to 50 g/L of the electrolyte solution, and (ii) a soluble silver C 1 -C 6 -alkane sulfonate or C 1 -C 6 -alkanol sulfonate at a concentration of 50 to 200 g/L of the electrolyte solution.
  • the electrolyte solution comprises (i) a C 1 -C 6 -alkane sulfonic acid or alkanol sulfonic acid at a concentration in a range of 5 to 30 g/L, preferably 10 to 20 g/L of the electrolyte solution, and (ii) a soluble silver C 1 -C 6 -alkane sulfonate or C 1 -C 6 -alkanol sulfonate at a concentration of 60 to 150 g/L of the electrolyte solution, calculated as silver ions.
  • the electrolyte solution comprises (i) a C 1 -C 6 -alkane sulfonic acid or alkanol sulfonic acid at a concentration in a range of 5 to 30 g/L, preferably 10 to 20 g/L of the electrolyte solution, and (ii) a soluble silver C 1 -C 6 -alkane sulfonate or C 1 -C 6 -alkanol sulfonate at a concentration of 80 to 120 g/L of the electrolyte solution, calculated as silver ions.
  • the present invention provides a process for production of copper powder in an electrolytic cell comprising an anode made of copper, a cathode and an electrolyte solution, which comprises
  • the electrolyte solution comprises (i) a C 1 -C 6 -alkane sulfonic acid or alkanol sulfonic acid at a concentration in a range of 80 to 200 g/L, preferably 100 to 160 g/L of the electrolyte solution, and (ii) a soluble silver C 1 -C 6 -alkane sulfonate or C 1 -C 6 -alkanol sulfonate at a concentration of 5 to 30 g/L of the electrolyte solution, calculated as copper ions.
  • the electrolyte solution comprises (i) a C 1 -C 6 -alkane sulfonic acid or alkanol sulfonic acid at a concentration in a range of 80 to 200 g/L, preferably 100 to 160 g/L of the electrolyte solution, and (ii) a soluble silver C 1 -C 6 -alkane sulfonate or C 1 -C 6 -alkanol sulfonate at a concentration of 5 to 15 g/L of the electrolyte solution, calculated as copper ions.
  • the copper powder obtained or obtainable by the process according to the present invention has a particle size D 50 in the range of 20 to 120 microns ( ⁇ m), preferably 30 to 100 ⁇ m, more preferably 40 to 90 ⁇ m, most preferably 40 to 80 ⁇ m.
  • the silver powder obtained or obtainable by the process according to the present invention has a particle size D 50 in the range of 100 to 600 microns ( ⁇ m), preferably 150 to 500 ⁇ m, more preferably 200 to 400 ⁇ m.
  • the silver powder obtained or obtainable by the process according to the present invention has a particle size D 90 in the range of 200 to 1,000 microns ( ⁇ m), preferably 400 to 800 ⁇ m.
  • D 90 is the diameter at which 90% of the total number of particles as characterized consists of particles with a diameter less than this value, as measured by a particle size laser analyzer.
  • the present specification also describes the use of an alkane sulfonic acid or alkanol sulfonic acid in an electrolyte solution for production of a silver or copper powder by electrolytic deposition.
  • the particle size D 50 of the copper powder is 81.6 ⁇ m.
  • the bath voltage is 2.5 V
  • the current efficiency ( ⁇ ) is 85.1%
  • the electrical energy consumption (W) is 2476 kW ⁇ h/t.
  • the bath voltage is 2.35 V
  • the current efficiency ( ⁇ ) is 89.16%
  • the electrical energy consumption (W) is 2222 kW ⁇ h/t.
  • the particle size D 50 of the copper powder is 78.4 ⁇ m.
  • the bath voltage is 2.2 V
  • the current efficiency ( ⁇ ) is 91.53%
  • the electrical energy consumption (W) is 2026 kW ⁇ h/t.
  • the particle size D 50 of the copper powder is 46.3 ⁇ m.
  • Copper sulfate pentahydrate was dissolved in an aqueous sulfuric acid solution to obtain a solution containing 12 g/L copper ions and 142 g/L free sulfuric acid as the electrolyte solution.
  • the solution was poured into the electrolytic cell and kept at a temperature of 25 °C.
  • An anode of phosphorus copper plate and a cathode of titanium plate were arranged in the electrolytic cell at a distance of 5 cm.
  • the electrolytic deposition was conducted by applying a direct current with a current density of 13 A/dm 2 for 15 minutes. Then, the obtained copper particles were removed from the cathode and isolated from the electrolyte solution.
  • the collected copper particles were filtered with vacuum filtration and washed by DI water, dried at a temperature of 60 °C in a vacuum drying oven, and then subjected to a reduction treatment by heating to 500 °C in a reducing atmosphere of hydrogen.
  • the copper powder has a particle size D 50 of 99.3 ⁇ m.
  • Black Ag 2 O was dissolved in an aqueous diluent solution of methanesulfonic acid (MSA) to provide a solution containing 108 g/L of silver ions and 15.25 g/L of free methanesulfonic acid as the electrolyte solution.
  • MSA methanesulfonic acid
  • the solution was poured into the electrolytic cell and kept at a temperature of 50 °C.
  • An anode of pure silver plate and a cathode of stainless steel plate were arranged in the electrolytic cell at a distance of 3.5 cm.
  • the electrolytic deposition was conducted by applying a direct current with the current density of 5 A/dm 2 for 15mins.
  • the obtained silver particles were removed from the cathode and isolated from the electrolyte solution.
  • the collected silver particles were filtered with vacuum filtration and washed by DI water, dried at a temperature of 60 °C in a vacuum drying oven.
  • the bath voltage is 1.23V, as determined by Kocour power supply, the current efficiency ( ⁇ ) is 98% and the electrical energy consumption (W) is 312 kW ⁇ h/t.
  • Granular crystals were observed via SEM for the silver powder, as shown in Figure 3 .
  • the particle size D 50 of the silver powder is 328.8 ⁇ m and D 90 is 525.4 ⁇ m.
  • the particle size D 50 of the silver powder is 571.5 ⁇ m and D 90 is 920.1 ⁇ m.
  • the bath voltage is 1.11V
  • the current efficiency ( ⁇ ) is 96%
  • the electrical energy consumption (W) is 287 kW ⁇ h/t.
  • the particle size D 50 of the silver powder is 395.2 ⁇ m and D 90 is 648.1 ⁇ m.
  • the particle size D 50 of the silver powder is 340.3 ⁇ m and D 90 is 1167.3 ⁇ m.
  • the silver powders produced according to the present invention at a temperature of above 40 °C have particle sizes at least comparable to those of the silver powders produced conventionally with the nitric acid electrolyte system.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (8)

  1. Procédé de production d'une poudre de métal dans une cellule électrolytique comprenant une anode composée du métal, une cathode et une solution électrolytique, qui comprend
    a) une dissolution anodique pour former des ions du métal dans la solution électrolytique et un dépôt cathodique de particules métalliques à partir de la solution électrolytique,
    b) l'élimination des particules métalliques de la cathode dans la solution électrolytique, et
    c) l'isolement des particules métalliques de la solution électrolytique,
    dans lequel
    - le métal est le cuivre ou l'argent, et
    - la solution électrolytique comprend (i) un acide alcanesulfonique ou un acide alcanolsulfonique et (ii) un sel métallique soluble d'un acide alcanesulfonique ou d'un acide alcanolsulfonique.
  2. Procédé selon la revendication 1, dans lequel l'acide alcanesulfonique est choisi parmi les acides alcanesulfoniques en C1-C12, de préférence les acides alcanesulfoniques en C1-C6.
  3. Procédé selon la revendication 1, dans lequel l'acide alcanolsulfonique est choisi parmi les acides alcanolsulfoniques en C2-C12, de préférence les acides alcanolsulfoniques en C2-C6.
  4. Procédé selon la revendication 2, dans lequel l'acide alcanesulfonique est choisi parmi l'acide méthanesulfonique, l'acide 1-éthanesulfonique, l'acide 1-propanesulfonique, l'acide 2-propanesulfonique, l'acide 1-butanesulfonique, l'acide 2-butanesulfonique, l'acide 1-pentanesulfonique, l'acide 1-hexanesulfonique, l'acide 1-décanesulfonique, l'acide 1-dodécanesulfonique, l'acide méthanedisulfonique, l'acide 1,1-éthanedisulfonique, l'acide 1,2-éthanedisulfonique, l'acide 1,1-propanedisulfonique, l'acide 1,3-propanedisulfonique, l'acide 1,1-butanedisulfonique, l'acide 1,4-butènedisulfonique et leurs combinaisons.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel l'étape a) est effectuée à une température dans la plage de 20 °C à 70 °C, de préférence de 30 °C à 60 °C, plus préférablement de 40 à 50 °C.
  6. Procédé selon la revendication 5, dans lequel une poudre d'argent est produite et l'étape a) est effectuée à une température dans la plage de 40 à 50 °C, de préférence de 45 à 50 °C.
  7. Procédé selon la revendication 5, dans lequel une poudre de cuivre est produite et l'étape a) est effectuée à une température dans la plage de 40 à 50 °C.
  8. Procédé selon l'une quelconque des revendications 1 à 7, qui comprend en outre une étape d'anti-oxydation des particules métalliques, de préférence une étape de réduction sous une atmosphère d'hydrogène.
EP22760941.9A 2021-08-13 2022-08-03 Procédé de production électrolytique de poudre métallique Active EP4384657B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2021112443 2021-08-13
PCT/EP2022/071854 WO2023016896A1 (fr) 2021-08-13 2022-08-03 Procédé de production électrolytique de poudre métallique

Publications (3)

Publication Number Publication Date
EP4384657A1 EP4384657A1 (fr) 2024-06-19
EP4384657B1 true EP4384657B1 (fr) 2025-10-08
EP4384657C0 EP4384657C0 (fr) 2025-10-08

Family

ID=77520464

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22760941.9A Active EP4384657B1 (fr) 2021-08-13 2022-08-03 Procédé de production électrolytique de poudre métallique

Country Status (8)

Country Link
US (1) US20240344221A1 (fr)
EP (1) EP4384657B1 (fr)
JP (1) JP2024529675A (fr)
KR (1) KR20240038984A (fr)
CN (1) CN117813420A (fr)
AU (1) AU2022325439A1 (fr)
TW (1) TW202314047A (fr)
WO (1) WO2023016896A1 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3816241B2 (ja) * 1998-07-14 2006-08-30 株式会社大和化成研究所 金属を還元析出させるための水溶液
JP2003342775A (ja) * 2002-05-24 2003-12-03 Murata Mfg Co Ltd 銀粉末の製造方法、及び銀粉末、並びに電子部品
EP3083016B1 (fr) * 2013-12-20 2020-07-29 Greene Lyon Group Inc. Procédé et appareil de récupération de métaux nobles, y compris de récupération de métaux nobles provenant de déchets plaqués et/ou de déchets remplis
CN106629738B (zh) * 2017-01-12 2019-03-22 东莞珂洛赫慕电子材料科技有限公司 一种从晶体硅太阳能板中提取银的方法

Also Published As

Publication number Publication date
KR20240038984A (ko) 2024-03-26
TW202314047A (zh) 2023-04-01
AU2022325439A1 (en) 2024-02-22
EP4384657A1 (fr) 2024-06-19
JP2024529675A (ja) 2024-08-08
WO2023016896A1 (fr) 2023-02-16
EP4384657C0 (fr) 2025-10-08
US20240344221A1 (en) 2024-10-17
CN117813420A (zh) 2024-04-02

Similar Documents

Publication Publication Date Title
US20190048483A1 (en) Producing lithium directly from lithium feed sources
CN104018186B (zh) 一种铜铟镓硒的回收方法
JP4519294B2 (ja) インジウムの回収方法
US4992149A (en) Process for the simultaneous recovery of manganese dioxide and zinc
JP2019052329A (ja) 低品位銅アノードの電解精錬方法およびそれに用いる電解液
KR20120041403A (ko) Ｐｂ-ｆｒｅｅ 폐솔더로부터 유가 금속의 회수방법
JP7122315B2 (ja) 電極及びその製造方法並びに再生電極の製造方法
CN110629252B (zh) 一种电解精炼制备金属铜的方法
CN210683962U (zh) 一种硝酸退镀液循环再利用系统
Bo et al. Purification of crude indium by two-stage cyclone electrowinning
EP4384657B1 (fr) Procédé de production électrolytique de poudre métallique
Popescu et al. The use of deep eutectic solvents ionic liquids for selective dissolution and recovery of Sn, Pb and Zn from electric and electronic waste (WEEE)
JP5780230B2 (ja) ガリウムの回収方法
CN106987869B (zh) 电解碱性蚀刻废液用的混合添加剂及用其制备铜粉的方法
DE2924143C2 (de) Verfahren zum galvanischen Abscheiden von Metall
KR102211986B1 (ko) 스크랩으로부터의 금속의 회수 방법
JP2012092447A (ja) コバルトの電解採取方法
Dong Gallium recovery by cyclone electrowinning from alkaline electrolyte with titanium cathode
CN117626368A (zh) 利用咪唑类双氰胺根离子液体电沉积金同步再生碘的方法
JP2002201025A (ja) 水酸化インジウム又はインジウムの回収方法
CN114956154A (zh) 一种酸性含铜液循环回收利用并制备氧化铜纳米线的方法
JP2622019B2 (ja) 粒状銅微粉末の製造方法
CN111893514A (zh) 一种电解碱性蚀刻液回收铜用的添加剂及使用其制备铜的方法
CN109881217A (zh) 锰电积用碳纤维基非晶态Pb-Mn-RuOx梯度阳极材料及制备方法
CN121802483A (zh) 一种硝酸盐-液氨溶液回收三元锂电池中镍钴金属的方法

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20240313

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20250409

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Ref country code: CH

Ref legal event code: F10

Free format text: ST27 STATUS EVENT CODE: U-0-0-F10-F00 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20251008

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602022022719

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

U01 Request for unitary effect filed

Effective date: 20251023

U07 Unitary effect registered

Designated state(s): AT BE BG DE DK EE FI FR IT LT LU LV MT NL PT RO SE SI

Effective date: 20251030

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251008

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20260108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251008

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20260108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20260208

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251008