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WO2025043273A1 - Récupération de métaux de valeur à partir de concentrés complexes - Google Patents

Récupération de métaux de valeur à partir de concentrés complexes Download PDF

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Publication number
WO2025043273A1
WO2025043273A1 PCT/AU2024/050686 AU2024050686W WO2025043273A1 WO 2025043273 A1 WO2025043273 A1 WO 2025043273A1 AU 2024050686 W AU2024050686 W AU 2024050686W WO 2025043273 A1 WO2025043273 A1 WO 2025043273A1
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Prior art keywords
copper
arsenic
process according
liquor
iron
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Inventor
Raymond Shaw
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Minetometal Pty Ltd
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Minetometal Pty Ltd
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Priority claimed from AU2023902748A external-priority patent/AU2023902748A0/en
Application filed by Minetometal Pty Ltd filed Critical Minetometal Pty Ltd
Publication of WO2025043273A1 publication Critical patent/WO2025043273A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C22B1/06—Sulfating roasting
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • 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
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • 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
    • C22B11/00—Obtaining noble metals
    • C22B11/08—Obtaining noble metals by cyaniding
    • 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
    • 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
    • C22B15/0084—Treating solutions
    • 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
    • C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
    • 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
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
    • 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
    • C22B3/32—Carboxylic acids
    • C22B3/326—Ramified chain carboxylic acids or derivatives thereof, e.g. "versatic" acids
    • 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
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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
    • C22B59/00—Obtaining rare earth metals
    • 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
    • C22B7/001—Dry processes
    • C22B7/002—Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
    • 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
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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

  • This invention relates to a novel process for treating complex materials to recover valuable metals contained in marketable products where the valuable metals present are commonly copper and/or nickel and/or cobalt and/or molybdenum and/or lithium and/or one or more rare earth metals.
  • ores In addition to the primary metal many ores contain impurities such as arsenic and/or radionuclides which are difficult to separate from the target metals and report as impurities in concentrates that are produced and can be of sufficient concentration to hinder or prevent processing of the concentrates through to metal.
  • impurities such as arsenic and/or radionuclides which are difficult to separate from the target metals and report as impurities in concentrates that are produced and can be of sufficient concentration to hinder or prevent processing of the concentrates through to metal.
  • Arsenic is a major problem in the non-ferrous metals industry as many of the ores contain significant concentrations of arsenic which typically reports into concentrates that are produced for further treatment. The amount of arsenic in these materials far exceeds the global market for arsenic and therefore the arsenic must be disposed of safely such that it does not cause contamination of the air, soil or water at either the mine or the processing plant.
  • arsenic compounds such as ferric arsenate and/or calcium arsenate and dispose of these into a suitable repository such as controlled landfill and/or on conjunction with other residues and tailings.
  • a suitable repository such as controlled landfill and/or on conjunction with other residues and tailings.
  • the formation of these compounds is quite complex and typically adds extra processing steps and costs to the metal processing.
  • the arsenic typically reports in the ore as mixed metal sulphides such as enargite and/or tennantite which have proven very difficult to separate from other more valuable minerals such as chalcopyrite and bornite.
  • mixed metal sulphides such as enargite and/or tennantite which have proven very difficult to separate from other more valuable minerals such as chalcopyrite and bornite.
  • enargite and/or tennantite which have proven very difficult to separate from other more valuable minerals such as chalcopyrite and bornite.
  • Radionuclides present a similar problem to arsenic in that they are very difficult to separate from the target metals by physical processing. In some cases the concentrations are high enough to warrant their recovery by adding hydrometallurgical processing but in selected cases the concentrations are too low to justify recovery but are high enough to be a barrier to selling the concentrate to an external smelter.
  • the inventors have found that by controlling the roasting step to match the composition of the feed material and achieve the desired reactions the calcine from the roast can be processed hydrometallurgically to recover the valuable metals in forms suitable for sale. This is most commonly used for copper sulphide concentrates but is also applicable to cocnentrates where nickel and/or cobalt are the most valuable metals present.
  • the process is operated such that almost all of the copper is recovered whilst fixing the arsenic as an inert iron arsenate.
  • the ore is processed using flotation separation to give a copper concentrate with low arsenic levels suitable for sale to a smelter, and a copper concentrate with high arsenic levels which is treated using this novel process.
  • the roasting stage is carried out with added lime at a temperature in the range from 400C to 700C and more preferably in the range from 550C to 650C.
  • the lime is added such that the molar ratio of Ca/S in the feed materials is >0.3 and more preferably >0.5.
  • the calcine typically contains a mix of copper arsenate, copper sulphate, copper oxide and iron oxide plus unreacted gangue oxides and silicates.
  • a part of the arsenic may also be present as iron arsenate and/or calcium arsenate.
  • the calcine is leached in an ammonia ammonium chloride liquor typically containing from 20-100g/l NH3 and from 20- 100g/l NH4C1 to dissolve the copper present as copper oxide and/or copper sulphate whilst leaving the arsenate compounds in the residue.
  • the copper is then precipitated from the pregnant leach liquor by evaporating off some of the ammonia and/or by cooling and/or by adding an alkali such as lime.
  • the iron arsenate precipitate is separated from the liquor and the liquor is then further processed to recover the copper from solution. This can be done using conventional technology such as solvent extraction - electrowinning but is more is preferably done by adding more alkali to raise the PH to around 6 and precipitate the copper.
  • the precipitate is then separated and in one embodiment is recycled within the process most commonly such that the copper is recovered through the ammonia - ammonium leaching stage either directly or by adding to the roaster.
  • An alternative in some cases is to add the copper precipitate from this step to the low arsenic concentrate to increase the grade and allow the copper to be recovered by sale to a smelter.
  • a further alternative is to use this precipitate as feed to produce copper chemicals such as copper sulphate which can be done through additional process steps and/or by sale to an external chemical company.
  • the iron arsenate precipitate can be disposed of as an inert compound but in some cases will be recycled to the roaster to improve the properties and enhance the stability when being disposed of.
  • Ferric arsenate in calcine does not dissolve in either the ammonia - ammonium chloride or the dilute sulphuric acid and hence the recycle does not affect any of the process steps.
  • complex ores containing economic levels of copper, nickel, cobalt, molybdenum and rare earth elements are processed to give a mixed metal concentrate which is fed to the roaster.
  • the feed commonly has sufficient sulphur present to enable the formation of the desired sulphates but if necessary the sulphur level can be increased by the addition of high sulphur material such as pyrite and/or conventional copper concentrate.
  • This feed material is roasted at a temperature of between 400C and 700C with sufficient air to convert the sulphides to sulphates and if necessary lime is added to react with part of the sulphur to form calcium sulphate to both control the oxygen potential in the roaster and to minimize the amount of sulphur dioxide being given off in the flue gas.
  • the calcine from the roaster is leached at a PH in the range of 6-8 (a neutral leach) to dissolve soluble metal sulphates such as cobalt sulphate, nickel sulphate and REE sulphates such a cerium sulphate. Copper present as oxide and/or sulphate and/or arsenate is not soluble at this PH and does not leach. Molybdenum and iron oxides also do not leach under these conditions.
  • the solid residue from the neutral leach is then leached with caustic soda which dissolves the molybdenum present but leaves the copper and iron unreacted in the solid residue.
  • the leach liquor is separated from the solids using conventional technology, most commonly filtration, and further processed to give a suitable molybdenum product such as molybdenum trioxide and/or molybdenum metal.
  • the calcine is leached with caustic soda prior to the neutral leach to dissolve the molybdenum and where present lithium and this leach liquor is separated and further processed to give separate molybdenum and lithium products.
  • the copper containing solid residue is then leached in an ammonia - ammonium chloride liquor using the technology described in PCT/AU2022/050188 to produce copper hydroxy chloride and/or copper oxide and/or copper metal and to recover precious metals such as gold and silver. If the residue contains significant levels of arsenic as copper arsenate then following the ammonia - ammonium chloride leach a dilute acid leach followed by iron arsenate precipitation is included as discussed previously.
  • the leach liquor from the neutral leach containing nickel, cobalt and rare earth metal is then processed through one or more solvent extraction stages to separate the metals and give marketable products. Most commonly the cobalt and nickel are removed first using commercial reagents such a Cyanex-272 and/or Versatic 10 and stripped into acid liquors for subsequent recovery.
  • a simpler flowsheet can be used.
  • the roasting stage is used to convert the metals to their leachable forms and the calcine is first subject to a caustic leach to dissolve the molybdenum for recovery.
  • the solid residue is then leached in an alkaline ammonia liquor most commonly ammonia ammonium chloride but other ammonium salts such as ammonium sulphate or ammonium carbonate can be used.
  • the conditions for this leach are set to dissolve all of the target metals leaving unwanted gangue, including iron oxides, for disposal.
  • sulphide precipitation using a sulphur source such as H2S gas or NaSH or Na2S is used to give a mixed metal sulphide precipitate which has sufficient contained value to be sold to, and/or custom smelted, in existing smelters.
  • the H2S required can be purchased externally or more preferably is generated within the process using one or more anaerobic bioreactors where sulphate present in the liquor reduces to form gaseous H2S.
  • the liquor from the sulphide precipitation stage is then passed to a rare earth recovery section where solvent extraction can be used to recover the individual metals.
  • An alternative is to precipitate the rare earth metals as a mixed oxide by the addition of oxalic acid or a suitable alternative and to sell the mixed oxide.
  • Sulphation roasting can also be used for materials such a black mass from batteries and/or electronic waste and/or waste from fabrication of finished products even though these contain little or no sulphur by combining the materials with a suitable sulphur source.
  • the sulphur source preferably contains valuable metals that can also be recovered.
  • the preferred sulphur source is a metal sulphide concentrate containing recoverable levels of one or more of copper, nickel cobalt or molybdenum.
  • the sulphation roasting of the blended material converts all the metal components into compounds that can be recovered by leaching and while utilizing nonmetallic components as fuels to minimize the amount of solid residue which requires disposal.
  • the flowsheet of the hydrometallurgical process used for the calcine varies depending upon the metals present. The simplest process is to leach the lithium and/or molybdenum and/or manganese at high PH using caustic soda and/or aqueous ammonia and then filter off the leach liquor for recovering the molybdenum and/or lithium and/or manganese then leaching the residue in ammonia-ammonium chloride to dissolve copper, nickel and cobalt and recovering these as a mixed metal sulphide by precipitation with H2S.
  • the lithium and molybdenum are recovered from the high PH liquor most commonly by selective precipitation through neutralization and/or carbonate precipitation.
  • the calcine may best be leached in dilute sulphuric acid at PH where the copper sulphate, nickel sulphate and cobalt sulphate are soluble but the iron in the calcine if present as ferric iron such as in hematite does not dissolve.
  • the preferred PH is greater than PH of 2 and more preferably greater than 2.3.
  • the liquor from this leach can then be processed to recover the metals by precipitation to raise the PH to around PH 8 either in a single step or in stages.
  • the preferred chemical for increasing the PH is magnesium carbonate as the magnesium reacts to form magnesium sulphate which is soluble in the liquor and does not contaminate the metal precipitates.
  • the magnesium sulphate liquor can then be further processed using bioreactors to recover the magnesium carbonate and sulphuric acid for reuse.
  • the preferred system is to first use an anaerobic bioreactor to convert the sulphate to elemental sulphur and/or hydrogen sulphide gas and/or metal sulphides and precipitate the magnesium as magnesium carbonate and then treat the hydrogen sulphide gas and if warranted any elemental sulphur or metal sulphides in an aerobic bioreactor to oxiidise them to sulphates, mainly as sulphuric acid, which can be returned to the leach.
  • magnesium carbonate to precipitate the metals as oxide/hydroxides from dilute sulphuric acid liquor with subsequent regeneration of the magnesium carbonate and sulphuric acid using bioreactors can also be used in other situations such as for treating liquor from heap leaching, ROM dump leaching and acid main drainage.
  • the concentrate is primarily a nickel sulphide concentrate which contains significant arsenic making it unattractive to conventional smelters
  • the concentrate is blended with material containing elements that can readily form arsenates such as copper and/or iron and/or calcium such that the arsenic present forms the arsenate and remains in the calcine while the nickel sulphide oxidises to a leachable form preferably nickel sulphate and/or nickel oxide.
  • the calcine is then processed using a mix of neutral, alkaline and acid leaching as described for the complex concentrate.
  • the preferred materials added to provide the arsenate forming metals are copper concentrate and/or pyrite concentrate as these also provide sulphur to assist in nickel sulphate formation and energy for use in the process plant.
  • Figure 1 shows the flowsheet as described in embodiment one where the complex sulphide concentrate is sulphation roasted at 600C in an air - sulphur dioxide atmosphere to convert the metals present to oxides an/or sulphates.
  • the calcine is then leached at PH around 7 in water and the slurry then filtered to give solids stream and a liquid stream.
  • the solids stream is then leached with caustic soda to dissolve the molybdenum present, and the slurry again filtered to give a copper rich residue and a sodium molybdate containing liquor.
  • the liquor is further processed to give molybdenum trioxide and/or molybdenum metal and/or other marketable molybdenum chemicals.
  • the copper rich residue is leached with ammonia-ammonium chloride liquor and the slurry filtered to leave a residue for disposal and/or processing to recover any PGM’s present and a copper rich liquor from which copper containing crystals are precipitated by stripping off part of the ammonia.
  • the liquor from the initial PH 7 leach passes to multiple solvent extraction stages to separate out the individual metals present.
  • the cobalt and nickel are recovered first with the raffinate form this passing to staged solvent extraction to give individual rare earth oxide products.
  • Figure 2 shows the flowsheet as described in embodiment two where the complex sulphide concentrate is sulphation roasted at 600C in an air - sulphur dioxide atmosphere to convert the metals present to oxides an/or sulphates.
  • the calcine is then leached in caustic soda and the slurry then filtered to give solids stream and a liquid stream.
  • the solids stream is then leached with caustic soda to dissolve the molybdenum present, and the slurry filtered to give a sodium molybdate containing liquor and a solid residue.
  • the liquor is further processed to give molybdenum trioxide and/or molybdenum metal and/or other marketable molybdenum chemicals.
  • the residue is leached with ammonia-ammonium chloride liquor at moderate PH and the slurry filtered to leave a residue for disposal and/or processing to recover any PGM’ s present and a metal rich liquor, from which copper containing crystals are precipitated by stripping off part of the ammonia.
  • the copper and/or cobalt and/or nickel in the liquor are precipitated as a high grade mixed metal sulphide which is filtered off and sold.
  • the liquor from the sulphide precipitation stage is then treated with oxalic acid or an alternative reactive chemical to precipitate the rare earth metals present as a high grade mixed oxide for sale to a rare earth’s processing plant.
  • FIG. 3 shows the process for recovering copper from an arsenic containing copper sulphide ore.
  • the copper ore is fed directly to a conventional concentrator where the sulphide minerals are separated from the gangue using a comminution - flotation circuit.
  • An additional flotation stage is included where the sulphide minerals present are further separated into a low arsenic copper concentrate suitable for sale to a conventional smelter and a high arsenic concentrate which requires further processing.
  • This high arsenic copper concentrate is fed to a roaster where a calcium source such as calcium oxide or more preferably calcium carbonate is added mixed with the sulphide concentrate such that as the material is roasted in an oxygen containing gas at -575C.
  • the sulphur present oxidises to sulphates and is retained in the calcine predominantly as a mix of calcium sulphate and copper sulphate. This removes the need for an acid plant.
  • the arsenic present is oxidized during the roast and predominantly reacts with copper in the concentrate to form copper arsenate and is retained in the calcine.
  • the gas from the roaster is scrubbed with lime to remove any sulphur containing gases and also capture any arsenic and other metals present.
  • the solids for the scrubber are then returned to the roaster to make use of excess lime and for any arsenic present to react with iron to convert it to ferric arsenate.
  • the crystals are filtered and washed and hydrolysed by mixing with a dilute ammonium hydroxide solution to hydrolyse the copper hydroxy chloride present to cupric oxide.
  • the dilute ammonia solution also dissolves traces of unwanted impurities that are precipitated with, or more generally entrained, in the crystals.
  • the pure cupric oxide crystals are then filtered of, washed in pure hot water and passed to the reduction stage. In the reduction stage the crystals pass through a rotary kiln held at a temperature of -250C with hydrogen gas continually fed into the rotary kiln to reduce the cupric oxide to copper metal which is the desired product.
  • the sulphur present oxidises to sulphates and is retained in the calcine predominantly as a mix of calcium sulphate and copper sulphate. This removes the need for an acid plant.
  • the arsenic present is oxidized during the roast and predominantly reacts with copper in the concentrate to form copper arsenate and is retained in the calcine.
  • the gas from the roaster is scrubbed with lime to remove any sulphur containing gases and also capture any arsenic and other metals present.
  • the solids for the scrubber are then returned to the roaster to make use of excess lime and for any arsenic present to react with iron to convert it to ferric arsenate.
  • the acidic liquor containing copper, arsenic and iron is partially neutralized using lime to raise the PH to ⁇ 2 and precipitate the majority of the arsenic present as ferric arsenate.
  • the slurry is filtered to separate the iron arsenate which is returned to the roaster to improve the form of the iron arsenate and leave a high copper liquor which is then further neutralized to precipitate the copper as a copper hydroxide/oxide.
  • the copper precipitate is filtered off and added to the low arsenic concentrate for sale to a smelter.
  • Figure 5 shows the flowsheet where a complex sulphide concentrate containing valuable copper, nickel and cobalt is blended with black mass from recycled lithium ion batteries which also contains valuable copper, nickel and cobalt as well as lithium and the blend is sulphation roasted at 600C in an air - sulphur dioxide atmosphere to convert the metals present to oxides and/or sulphates.
  • the calcine is then leached in caustic soda at around 4M/1 to dissolve the lithium and leave the other metals in the solid residue.
  • the slurry then filtered to give solids stream and a liquid stream. Magnesium carbonate is added to the liquid stream to precipitate the lithium as lithium carbonate suitable for sale.
  • the slurry is filtered to separate the iron arsenate which is returned to the roaster to improve the form of the iron arsenate and leave a high copper liquor which is then further neutralized to precipitate the copper as a copper hydroxide/oxide.
  • the copper precipitate is filtered off and added to the low arsenic concentrate for sale to a smelter.
  • the copper rich pregnant liquor is fed to an ammonia stripping - crystallization step where the ammonia is stripped off by heating the liquor to boiling point.
  • the pregnant liquor continues to boil as it is heated and this drives off ammonia gas in an ammonia - water gas. As the ammonia concentration drops the copper solubility decreases and copper containing crystals which contain some copper hydroxy chloride precipitate.
  • the crystal containing liquor is then cooled to 25C to precipitate more crystals and filtered to separate the crystal from the spent liquor.
  • the ammonia - water vapour gas passes into an absorption column where it is contacted with the cooled spent liquor from the crystallisation stage and the ammonia and water are recaptured for recycle to the leaching stage.
  • the crystals are filtered and washed and hydrolysed by mixing with a dilute ammonium hydroxide solution to hydrolyse the copper hydroxy chloride present to cupric oxide.
  • the dilute ammonia solution also dissolves traces of unwanted impurities that are precipitated with, or more generally entrained, in the crystals.
  • the pure cupric oxide crystals are then filtered off, washed and blended with the low arsenic concentrate for sale to a smelter.
  • Figure 9 shows the flowsheet for processing a complex sulphide concentrate containing valuable amounts of one or more of copper, cobalt, zinc and nickel where the cobalt, nickel and zinc and at least part of the copper are recovered from a dilute acid liquor by staged precipitation.
  • the calcine from the sulphation roast is leached in dilute sulphuric acid to dissolve the readily leachable sulphates.
  • the liquor is filtered from the solids and PH adjusted in two stages using magnesium carbonate. The first precipitation stage raises the PH to ⁇ 6 to precipitate the copper as copper hydroxide/copper oxide which is then filtered off to leave a magnesium sulphate rich liquor containing the nickel and cobalt.
  • More magnesium carbonate is added to raise the PH to ⁇ 8.4 to precipitate the nickel, zinc and cobalt as hydroxides leaving a magnesium sulphate rich liquor with low levels of the copper, cobalt and nickel.
  • the magnesium sulphate liquor is then passed to an anaerobic bioreactor where the sulphate is reduced to give hydrogen sulphide gas and magnesium carbonate precipitates and is recycled to the precipitation stages.
  • the hydrogen sulphide gas transfers to an aerobic bioreactor where to the hydrogen sulphide is oxidized to generate sulphuric acid to return to the dilute acid leach stage.
  • the PH is then raised to PH 6.2 to precipitate out the copper as copper oxide and/or copper hydroxide which is then filtered off to leave a magnesium sulphate rich liquor containing metals such as nickel, cobalt, and zinc. More magnesium carbonate is added to raise the PH to ⁇ 8.4 to precipitate any nickel, cobalt and zinc that are present as hydroxides leaving a magnesium sulphate rich liquor with low levels of the metals.
  • the magnesium sulphate liquor is then passed to an anaerobic bioreactor where the sulphate is reduced to give hydrogen sulphide gas and magnesium carbonate precipitates and is recycled to the precipitation stages.
  • the hydrogen sulphide gas transfers to an aerobic bioreactor where the hydrogen sulphide is oxidized to generate sulphuric acid to return to the dilute acid leach stage. Where there is excess sulphate in the system and there is no other use for the sulphuric acid being generated lime and/or limestone is added to precipitate part of the sulphate to retain the sulphur balance in the system.
  • the residue from the water leach were then further processed by leaching in ammonia - ammonium chloride liquor containing ⁇ 5 Og/1 NH3 and ⁇ 50g/l NH4C1 for 2 hours at 50C and the solids and liquids again separated.
  • the liquor from this leach was analysed and found to contain 40g/l Cu but no detectable Arsenic confirming that it was present at ⁇ lppm and not leached.
  • the solid residue from this leach was analysed and found to contain 240ppm Arsenic confirming that the arsenic was present in an inert form.
  • Example 4 [0049] A 16.3 gram sample of the residue from Example 3 was leached in 20g/l H2SO4 and the liquor analysed. The liquor analyses was used to construct a mass balance which showed that 85.5% of the copper, 95.5% of the arsenic and 17% of the iron in the feed sample dissolved in the acid. The slurry was filtered and a 50g/l sulphuric acid liquor added to the solids residue to dissolve further copper and arsenic. The residue from the leach was analysed and found to contain 0.3% copper, 0.1% arsenic and 13% iron. The mass balance from the residue analyses showed that 97.5% of the copper, 99.1% of the arsenic and 39% of the iron was extracted by the 2 stage acid lead.
  • Example 5 A mass balance was constructed across the roasting, water washing, ammonia - ammonium chloride and 2 stage acid leaches as described in examples 2-4 and found that for the entire process >99% of the copper was extracted into the liquors, >99% of the arsenic reported to the dilute sulphuric acid liquor and 34% of the iron reported to the dilute acid liquor.

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Abstract

Des matériaux complexes qui contiennent un mélange de métaux sont traités pour récupérer des métaux de valeur présents dans ces derniers, le procédé consistant à torréfier les matériaux dans des conditions dans lesquelles les métaux forment des composés qui peuvent être dissous dans des solutions alcalines contenant de l'acide dilué et/ou de l'eau et/ou de l'ammoniac, dans lesquelles les métaux peuvent être récupérés sous forme de produits commercialisables tout en laissant des éléments d'impuretés indésirables tels que de l'arsenic et des radionucléides sous la forme d'un résidu inerte afin de permettre leur élimination.
PCT/AU2024/050686 2023-08-25 2024-06-27 Récupération de métaux de valeur à partir de concentrés complexes Pending WO2025043273A1 (fr)

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AU2023902748A AU2023902748A0 (en) 2023-08-25 Recovering Metal Values from Complex Concentrates
AU2023902748 2023-08-25
AU2023903989 2023-12-08
AU2023903989A AU2023903989A0 (en) 2023-12-08 Recovering Metal Values from Arsenic Containing Feed Materials

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Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2741553A (en) * 1954-11-04 1956-04-10 Quebec Metallurg Ind Ltd Method for producing a matte from arsenical sulfide cobalt ores
US4457897A (en) * 1982-09-28 1984-07-03 Noranda Mines Limited Process for the selective dissolution of cobalt from cobaltite-pyrite concentrates
EP0155250A1 (fr) * 1984-03-06 1985-09-18 Boliden Aktiebolag Procédé de récupération des métaux de matériaux contenant du fer
US5254320A (en) * 1990-12-17 1993-10-19 A. Ahlstrom Corporation Method for roasting sulphide ores
US6248301B1 (en) * 1991-04-12 2001-06-19 Newmont Mining Corporation And Newmont Gold Company Process for treating ore having recoverable metal values including arsenic containing components
US20040156765A1 (en) * 2003-02-12 2004-08-12 Nichromet Extraction Inc. Gold and silver recovery from polymetallic sulfides by treatment with halogens
US20090148366A1 (en) * 2005-12-22 2009-06-11 Eric Girvan Roche Magnesium Oxide Recovery
US20090148365A1 (en) * 2005-12-22 2009-06-11 Eric Girvan Roche Recovery of Solid Magnesium Sulfate Hydrate
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JP2019007049A (ja) * 2017-06-26 2019-01-17 国立大学法人九州大学 選鉱方法
CN107723460B (zh) * 2017-10-23 2019-03-19 湖南华信稀贵科技股份有限公司 一种复杂铅锌铜矿的冶炼工艺
CN111996383A (zh) * 2020-08-25 2020-11-27 中南大学 一种搭配高砷物料分离铜渣中砷的方法
CN114277251A (zh) * 2021-12-24 2022-04-05 中南大学 一种分离和回收废弃锂电池中金属的方法
WO2022187893A1 (fr) * 2021-03-12 2022-09-15 Minetometal Pty Ltd Procédé hydrométallurgique de cuivre amélioré
CN115466845A (zh) * 2022-08-25 2022-12-13 广东邦普循环科技有限公司 一种从废旧锂离子电池中回收有价金属的方法
WO2023045331A1 (fr) * 2021-09-27 2023-03-30 湖南邦普循环科技有限公司 Procédé de récupération sélective de métal précieux dans une batterie au lithium-ion usagée
GR1010450B (el) * 2022-06-04 2023-04-28 Ηλιας Θεολογου Σταμπολιαδης Ανακτηση συμπυκνωματος νικελιου, κοβαλτιου απο φτωχα σιδηρονικελιουχα λατεριτικα μεταλλευματα

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2741553A (en) * 1954-11-04 1956-04-10 Quebec Metallurg Ind Ltd Method for producing a matte from arsenical sulfide cobalt ores
US4457897A (en) * 1982-09-28 1984-07-03 Noranda Mines Limited Process for the selective dissolution of cobalt from cobaltite-pyrite concentrates
EP0155250A1 (fr) * 1984-03-06 1985-09-18 Boliden Aktiebolag Procédé de récupération des métaux de matériaux contenant du fer
US5254320A (en) * 1990-12-17 1993-10-19 A. Ahlstrom Corporation Method for roasting sulphide ores
US6248301B1 (en) * 1991-04-12 2001-06-19 Newmont Mining Corporation And Newmont Gold Company Process for treating ore having recoverable metal values including arsenic containing components
US20040156765A1 (en) * 2003-02-12 2004-08-12 Nichromet Extraction Inc. Gold and silver recovery from polymetallic sulfides by treatment with halogens
US20090148366A1 (en) * 2005-12-22 2009-06-11 Eric Girvan Roche Magnesium Oxide Recovery
US20090148365A1 (en) * 2005-12-22 2009-06-11 Eric Girvan Roche Recovery of Solid Magnesium Sulfate Hydrate
CN102876892A (zh) * 2012-10-30 2013-01-16 杭州蓝普水处理设备有限公司 低铁高镁、高铁低镁红土镍矿用废稀硫酸浸出镍钴的方法
JP2019007049A (ja) * 2017-06-26 2019-01-17 国立大学法人九州大学 選鉱方法
CN107723460B (zh) * 2017-10-23 2019-03-19 湖南华信稀贵科技股份有限公司 一种复杂铅锌铜矿的冶炼工艺
CN111996383A (zh) * 2020-08-25 2020-11-27 中南大学 一种搭配高砷物料分离铜渣中砷的方法
WO2022187893A1 (fr) * 2021-03-12 2022-09-15 Minetometal Pty Ltd Procédé hydrométallurgique de cuivre amélioré
WO2023045331A1 (fr) * 2021-09-27 2023-03-30 湖南邦普循环科技有限公司 Procédé de récupération sélective de métal précieux dans une batterie au lithium-ion usagée
CN114277251A (zh) * 2021-12-24 2022-04-05 中南大学 一种分离和回收废弃锂电池中金属的方法
GR1010450B (el) * 2022-06-04 2023-04-28 Ηλιας Θεολογου Σταμπολιαδης Ανακτηση συμπυκνωματος νικελιου, κοβαλτιου απο φτωχα σιδηρονικελιουχα λατεριτικα μεταλλευματα
CN115466845A (zh) * 2022-08-25 2022-12-13 广东邦普循环科技有限公司 一种从废旧锂离子电池中回收有价金属的方法

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