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
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B15/00—Obtaining copper
  • C22B15/0063—Hydrometallurgy
  • C22B15/0065—Leaching or slurrying
  • C22B15/0067—Leaching or slurrying with acids or salts thereof
  • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
• • 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
  • C22B23/04—Obtaining nickel or cobalt by wet processes
  • C22B23/0407—Leaching processes
  • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
  • C22B23/043—Sulfurated acids or salts thereof
• • 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
  • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
  • C22B7/006—Wet processes
  • C22B7/007—Wet processes by acid leaching
• • 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
• • 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

Definitions

• cobalt and nickel containing raw materials and intermediates also contain quantities of copper that end up in leaching solutions after dissolving these materials.
• examples are, among others, mattes from primary smelting of ores, intermediate hydroxide and sulfide products from Cu, Co and Ni mining, certain metallic deep-sea nodules containing Co, Ni and Mn, white alloys produced during smelting of Co and Ni products, as well as wastes and production scrap generated during production or use of lithium- ion or nickel metal hydride batteries.
• EW electrowinning
• the Cu in the electrolyte is replenished in the process, for example by feeding a Cu-rich leach solution to the EW circuit or by sending the electrolyte from the EW operation back to the stripping section of a Cu-SX process.
• the Cu concentration thus remains on a high level throughout the process, and even variations in the concentration at entry and exit of the EW-cell are limited.
• EW can also be applied with the goal to deplete the Cu content in a Cu-bearing solution.
• a series of electrowinning cells are put in cascade, each operating at a decreasing Cu concentration (B.C. Wesstrom and O. Araujo, Optimizing a Cascading Liberator, T. T. Chen Honorary Symp. Hydrometall., Electrometall. Mater. Charact. Proc., 151, 2012).
• the primary objective is to remove the Cu from the stream, rather than producing a pure and valuable Cu product.
• a term used for this is "depletion Cu-EW".
• the physical quality of the deposited Cu is usually very poor, especially at lower Cu concentrations, and thus requires further refining.
• Cu-EW is often embedded in larger hydrometallurgical process schemes where downstream operations can only tolerate limited incoming Cu concentrations.
• a typical application is the recovery of Cu from bleed streams in which impurities are purged from the main circuit in conventional Cu electrorefining and EW operations.
• the acid concentration in such process schemes is rather high, such as from 350 to 400 g/L (A. Siegmund, S. Gadia, G. Leuprecht, P. Stantke, Proceedings of Copper 2013, 275-283).
• Cu electrorefining entails electrochemically dissolving copper from impure anodes into an electrolyte, and electrochemically plating pure copper from the electrolyte onto a cathode.
• WO19102765 describes a process, in which an alloy containing Cu, Ni and Co is used as anode in an electrolytic purification process. In this process, Cu, Ni and Co are dissolved into the electrolyte, followed by a deposition of Cu onto a cathode. In one example the Cu concentration is reduced from 10 to 1 g/L in a batch process by applying a very high current density of 1500 A/m ⁇ , resulting in a Cu product with a chemical purity of 99.9%. The physical characteristics of the Cu deposit are, however, not described. Under these high current densities, typically Cu powders are produced rather than dense deposits.
• the physical quality of a Cu deposit is mainly defined by the compactness of the sheet cathode (absence of porosity, cracks and voids) and by the smoothness of its surface (absence of dendrites, nodules and other protrusions).
• cathode geometries other than sheets or blanks are used, such as copper granules or copper mesh.
• the cell-geometry in the non-conventional RED-cell differs from classic design in having two compartments, separated by a membrane.
• the chemical quality of a Cu-deposit is determined in exactly the same way as in the conventional case, but the parameters for the physical quality needed to be redefined.
• New quality criteria for Cu-electrodeposits on a copper mesh cathode are proposed, among others also to solve the issue of a co-deposition of arsenic, present in the electrolyte.
• a first embodiment therefore describes a process for electrowinning of Cu from an aqueous acidic solution containing Cu and one or more of Ni and Co onto a cathode starting sheet, comprising the steps:
• - providing a copper electrowinning cell - electrowinning of Cu from an aqueous sulfuric acid solution at a temperature of 50 to 70 °C, wherein the concentration of sulfuric acid is 20 to 100 g/L, wherein the concentration of Cu is at least 2 g/L and at most 15 g/L, and wherein the aqueous acidic solution is free of organic additives;
• Electrowinning is the electrodeposition of metals that have been put in solution via a process commonly referred to as leaching done in a separate operation.
• the Cu-EW process is performed at low current densities and low Cu concentrations.
• the Cu concentration cannot be too low, otherwise no coherent deposit is formed. This requires a minimum concentration of Cu of about 2 g/L. On the other hand, a maximum concentration of Cu of about 15 g/L should not be exceeded, because otherwise a deposit with significant edge effects will be formed.
• organic additives we mean product families such as poly- and oligosaccharides (e.g. guar gum and modified starches), (poly)peptides (e.g. gelatin), poly(meth)acrylic acid, poly(meth)acrylate salts and esters, polyethers, fluoropolymers, polyacrylamides, alkyl sulfonates and other organosulfur and organonitrogen compounds, including their degradation products.
• poly- and oligosaccharides e.g. guar gum and modified starches
• poly(meth)acrylic acid e.g. gelatin
• poly(meth)acrylic acid e.g. gelatin
• poly(meth)acrylic acid e.g. gelatin
• poly(meth)acrylic acid e.g. gelatin
• poly(meth)acrylate salts and esters e.g. gelatin
• polyethers e.g. ethylene glycol dimethacrylate salts and esters
• a second embodiment describes a process, wherein the cathode starting sheet is a copper starter sheet or a stainless steel or titanium blank.
• Cathode starting sheets are used in electrowinning cells to deposit metals such as copper on a flat surface.
• Such cathode starting sheets are typically in the form of thin copper starter sheets or blanks, made of stainless steel or titanium.
• Cu deposited on a copper starter sheet can be harvested and be collected directly, ready for further processing. Copper deposited on a stainless steel or titanium blank is typically stripped (lifted) from this blank and then collected. In both cases it is important that the Cu-deposit is coherent and doesn't disintegrate, which would interfere with a proper and quantitative collection of the metal.
• the current density is below 200 A/m ⁇ , more preferably below 150 A/m ⁇ and even more preferably at 140 A/m ⁇ or less.
• the means for agitating comprise sparging with air or nitrogen, mechanical or ultrasonic agitation or forced circulation.
• Means for agitating is meant in the broadest possible way. Air sparging is frequently used, but air can be replaced by nitrogen or any other non-reactive gas, as the type of gas is less important than the effect it creates when flushed through the electrolytic solution. Gases which react with copper or any other compound of the solution obviously should be avoided in the EW-process.
• agitating can also be achieved with ultrasound or mechanical stirring or a forced circulation, for example by an optimized electrolyte injection, which results in whirling and mixing of the electrolyte solution.
• forced circulation can be found in Cooper et al. (W.C. Cooper, J. Appl. Electrochem. 15, 789-805, 1985).
• PCR periodic current reversal
• Air sparging is the preferred means for agitating.
• the copper electrowinning cell is a parallel plate cell.
• This cell type comprises a rectangular cell containing flat plate anodes and cathodes, which are placed alternatingly in the cell.
• Flat plates generally facilitate the recovery of copper.
• the H2SO4 has a preferred concentration of 40 to 80 g/L.
• Sulfuric acid is the preferred choice, because it is most often used in leaching operations, and most typically used in Cu-EW.
• the present invention works in significantly milder conditions (20 to 100 g/L H2SO4), preferably 40 to 80 g/L. This allows to treat leaching solutions, having mild acidities, and without the need for further acidification. It is also an advantage when having to neutralize Cu-depleted process solutions.
• the aqueous acidic solution containing Cu and one or more of Ni and Co is obtained by leaching of starting materials comprising Li-ion batteries or their waste.
• Leaching solutions originating from the recycling of batteries typically contain appreciable amounts of copper, as well as nickel and/or cobalt.
• the present process is therefore particularly advantageous to treat such leaching solutions.
• the aqueous sulfuric acid solution has a Ni concentration of at least 20 g/L.
• the aqueous sulfuric acid solution has a Co concentration of at least 5 g/L.
• Typical leach solutions from battery recycling have concentrations of Ni of at least 20 g/L, and of Co of at least 5 g/L. Such concentrations make them a valuable source for recovering the metals.
• the aqueous acidic solution containing Cu and one or more of Ni and Co is free of arsenic.
• Co-deposition of As together with Cu is a recurring problem for streams containing both, leading to a reduced chemical quality of the Cu-deposit.
• Li-ion batteries and their waste typically do not contain arsenic.
• Type-1 The deposit is coherent and dense (low porosity), showing very limited formation of nodules or dendrites at the edges.
• the Cu is uniformly deposited on the cathode surface.
• Type-2 The deposit is coherent and dense, but shows pronounced formation of nodules or dendrites at the edges. Thus, the Cu is not uniformly deposited on the cathode surface.
• Type-3 The deposit is porous and non-coherent. It adheres poorly to the cathode and can easily disintegrate.
• Examples 1 to 3 were performed as batch processes.
• Cu-EW beaker cell tests were performed in a beaker cell of 2.8 L connected to circulation tanks, containing 50 L of electrolyte. A flow rate of 4,2 L/h and a temperature of 60 °C were selected. Synthetic electrolyte with a composition as indicated in Table 1 was used (Cu and H2SO4 not shown).
• Comparative Example 2 The final Cu concentration is too high (35 g/L) and therefore results in Type-2 deposition.
• Comparative Example 3 The final Cu concentration is too low (1 g/L) and therefore results in Type-3 deposition.
• the electrolyte in the circulation tank was fed with electrolyte with a high Cu concentration (40 to 45 g/L) and low H2SO4 concentration (2 to 3 g/L).
• the composition of the electrolyte is indicated in Table 1. Sparging with air was applied underneath the cathode.
• Comparative Example 5 The Cu concentration is too high (20 g/L), which results in Type-2 deposition.
• Comparative Example 6 The current density is too high (225 A/m ⁇ ), which results in Type-3 deposition. Comparative Example 8: The temperature is too low (40°C), which results in Type-3 deposition.
• Comparative Example 11 The use of organic additives at high Cu-concentration results in Type-1 deposition.
• Comparative Example 12 The use of organic additives at low Cu concentration results in Type-3 deposition.

Landscapes

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

Applications Claiming Priority (2)

Publications (1)

Family

ID=84357840

Family Applications (1)

Country Status (8)

Family Cites Families (5)

• 2022
  • 2022-10-14 BE BE20225827A patent/BE1030447B1/nl active IP Right Grant
• 2023
  • 2023-10-04 AU AU2023358845A patent/AU2023358845A1/en active Pending
  • 2023-10-04 CA CA3266301A patent/CA3266301A1/en active Pending
  • 2023-10-04 EP EP23783431.2A patent/EP4573236A2/de active Pending
  • 2023-10-04 WO PCT/EP2023/077459 patent/WO2024078938A2/en not_active Ceased
  • 2023-10-04 KR KR1020257010795A patent/KR20250087539A/ko active Pending
  • 2023-10-04 CN CN202380065958.6A patent/CN119816627A/zh active Pending
  • 2023-10-04 JP JP2025516260A patent/JP2025532799A/ja active Pending

Also Published As

Similar Documents

Legal Events