US20190345580A1 - Leaching Copper-Containing Ores - Google Patents

Leaching Copper-Containing Ores Download PDF

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Publication number
US20190345580A1
US20190345580A1 US16/153,043 US201816153043A US2019345580A1 US 20190345580 A1 US20190345580 A1 US 20190345580A1 US 201816153043 A US201816153043 A US 201816153043A US 2019345580 A1 US2019345580 A1 US 2019345580A1
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additive
copper
ores
groups
leaching
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Inventor
Daniel Arthur Kittelty
Paul Leslie Brown
Ralph Peter Hackl
Pauline Maree Najjar
Anna Zonneveld
Jason Maurice Young
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Technological Resources Pty Ltd
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Technological Resources Pty Ltd
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Priority claimed from AU2018901583A external-priority patent/AU2018901583A0/en
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Assigned to HRL TECHNOLOGY GROUP PTY LTD reassignment HRL TECHNOLOGY GROUP PTY LTD ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ZONNEVELD, Anna
Assigned to TECHNOLOGICAL RESOURCES PTY. LIMITED reassignment TECHNOLOGICAL RESOURCES PTY. LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HACKL, RALPH PETER, KITTELTY, DANIEL ARTHUR
Assigned to EVOLVE SCIENTIFIC RECRUITMENT PTY LTD reassignment EVOLVE SCIENTIFIC RECRUITMENT PTY LTD ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YOUNG, Jason Maurice
Assigned to TECHSTAFF PTY LTD reassignment TECHSTAFF PTY LTD ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NAJJAR, Pauline Maree
Assigned to TECHNOLOGICAL RESOURCES PTY. LIMITED reassignment TECHNOLOGICAL RESOURCES PTY. LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BROWN, PAUL LESLIE
Priority to US16/364,453 priority Critical patent/US10563284B2/en
Assigned to TECHNOLOGICAL RESOURCES PTY. LIMITED reassignment TECHNOLOGICAL RESOURCES PTY. LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TECHSTAFF PTY LTD
Assigned to TECHNOLOGICAL RESOURCES PTY. LIMITED reassignment TECHNOLOGICAL RESOURCES PTY. LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: EVOLVE SCIENTIFIC RECRUITMENT PTY LTD
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Publication of US20190345580A1 publication Critical patent/US20190345580A1/en
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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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with 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
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/205—Treatment or purification of solutions, e.g. obtained by leaching using adducts or inclusion complexes
    • 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
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20—Bacteria; Culture media therefor
    • C12N1/205—Bacterial isolates
    • 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
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • 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
    • C22B15/0002—Preliminary treatment
    • C22B15/0004—Preliminary treatment without modification of the copper constituent
    • C22B15/0008—Preliminary treatment without modification of the copper constituent 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
    • 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
    • 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
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/09—Diamines
    • C07C211/10—Diaminoethanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/20—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton
    • C07C211/22—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton containing at least two amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12R—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
    • C12R2001/00—Microorganisms ; Processes using microorganisms
    • C12R2001/01—Bacteria or Actinomycetales ; using bacteria or Actinomycetales
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0073—Leaching or slurrying with acids or salts thereof containing nitrogen
    • 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
    • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
    • C22B3/1608—Leaching with acyclic or carbocyclic agents
    • C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
    • C22B3/1625—Leaching with acyclic or carbocyclic agents of a single type with amines
    • 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
    • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
    • C22B3/1666—Leaching with heterocyclic compounds
    • 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 leaching copper-containing ores.
  • the present invention relates particularly, although not exclusively, to leaching any one or more of (a) copper-containing ores (which may be in the form of agglomerates of ore fragments), (b) concentrates of the ores, and (c) tailings of the ores or concentrates produced for example by flotation or other downstream processing of ores or concentrates.
  • the present invention relates particularly, although not exclusively, to leaching copper-containing sulfidic ores, such as sulfidic ores that contain copper minerals such as chalcopyrite (CuFeS 2 ) and/or enargite (Cu 3 AsS 4 ).
  • the sulfidic ores may contain other copper minerals.
  • the present invention relates particularly, although not exclusively, to a method of leaching copper-containing ores, particularly copper-containing sulfidic ores, using an additive to enhance dissolution of copper in the ores.
  • the particle size of the ores is typically reduced from run-of-mine size, for example by crushing and grinding operations, to allow processing via heap leaching, vat leaching or reactor leaching options.
  • leaching processes involve the application of an acid and an oxidant to dissolve copper into solution. Copper is subsequently recovered from the acidic solution by a range of recovery options including solvent extraction and electrowinning (SX/EW), cementation onto more active metals such as iron, hydrogen reduction, and direct electrowinning. The acidic solution is regenerated and recycled to leach more copper from the ores. Leaching may be assisted by the use of microorganisms.
  • leaching may provide lower metal recoveries than other process options for recovering copper from sulfidic ores, such as milling and flotation, that produce copper-containing concentrates that are then smelted to produce copper metal.
  • the present invention was made in research and development work by a Group company of the applicant.
  • the present invention makes it possible to achieve higher recoveries of copper from copper-containing minerals in ores via an enhanced leaching mechanism.
  • the present invention is based on a realisation that leaching copper-containing ores or concentrates of the ores or tailings of the ores or concentrates produced for example by flotation or other downstream processing of ores or concentrates can be enhanced via the formation of a complex comprising (a) sulfur, that has originated from copper minerals in the ores, and (b) an additive.
  • the present invention is based on a realisation that leaching copper-containing ores or concentrates of the ores or tailings of the ores or concentrates can be enhanced via the formation of a complex between (a) sulfur, that has originated from copper minerals in the ores, and (b) an additive that results in an increase in dissolution rates.
  • the sulfur may be in a passivating layer on copper minerals
  • the complex may be a complex of the additive and sulfur in the passivating layer that breaks down the passivating layer or reduces the formation of the layer and therefore allows greater access for leaching copper from copper minerals.
  • This invention can be described as a “mechanism invention”.
  • the present invention is also based on a realisation that a particular group of nitrogen-containing complexing agents are effective additives for the above-described leaching method.
  • This invention can be described as an “additive-specific invention”.
  • the mechanism invention is a method of leaching copper-containing ores, such as copper-containing sulfidic ores that contain copper minerals such as chalcopyrite and/or enargite, or concentrates of the ores or tailings of the ores or concentrates, that includes leaching copper-containing ores or concentrates or tailings of the ores or concentrates with a leach liquor in the presence of an additive that enhances the dissolution of copper from copper minerals in the ores and concentrates by forming a complex between (a) sulfur, that has originated from copper minerals in the ores, and (b) the additive.
  • leaching copper-containing ores such as copper-containing sulfidic ores that contain copper minerals such as chalcopyrite and/or enargite
  • concentrates of the ores or tailings of the ores or concentrates that includes leaching copper-containing ores or concentrates or tailings of the ores or concentrates with a leach liquor in the presence of an additive that enhances the dissolution of copper from copper
  • the complex may comprise sulfur in a passivating layer on copper minerals and the additive, with the complex breaking down the passivating layer or reducing the formation of the layer and therefore allowing greater access for leaching copper from copper minerals.
  • the method may include any one of:
  • the additive may comprise a nitrogen-containing complexing agent that includes at least two nitrogen atoms spaced by two carbon atoms to permit the additive to form complexes between sulfur, that has originated from copper minerals in the ores, and the additive.
  • Each of the at least two nitrogen atoms in the additive may be present as a primary amine group, a secondary amine group or a tertiary amine group.
  • the additive may form complexes with copper(I), copper(II), iron(II), and iron(III) that has originated from the ores that enhance leaching of copper from copper minerals in the ores or concentrates, including the complexes set out below:
  • the following structures show possible complexes that can form between sulfur that has originated from copper minerals in the ores and the additive, where the additive is, for example, ethylenediamine.
  • the metal ion or sulfur is derived from the dissolution of the copper minerals in the ores or concentrates or tailings of the ores or concentrates, such as chalcopyrite or enargite.
  • the complex may form a ring or chain structure.
  • the formation of these complexes may be controlled and/or enhanced by the addition of an acid, such as sulfuric acid, and an oxidant or reductant.
  • the additive may react directly with the sulfur from the mineral to enhance leaching via reducing the activation energy, i.e. have a catalytic effect.
  • the additive-specific invention is a method of leaching copper-containing ores, such as copper-containing sulfidic ores that contain copper minerals such as chalcopyrite and/or enargite, or concentrates of the ores, that includes leaching copper-containing ores or concentrates or tailings of the ores or concentrates with a leach liquor in the presence of a nitrogen-containing organic complexing additive that forms a complex between sulfur, that has originated from copper minerals in the ore, and the additive.
  • leaching copper-containing ores such as copper-containing sulfidic ores that contain copper minerals such as chalcopyrite and/or enargite
  • concentrates of the ores that includes leaching copper-containing ores or concentrates or tailings of the ores or concentrates with a leach liquor in the presence of a nitrogen-containing organic complexing additive that forms a complex between sulfur, that has originated from copper minerals in the ore, and the additive.
  • the complex may comprise sulfur in a passivating layer on copper minerals and the additive, with the complex breaking down the passivating layer or reducing the formation of the layer and therefore allowing greater access for leaching copper from copper minerals during the method.
  • the additive be sufficiently water soluble to be able to enhance copper extraction into the leach solution.
  • the additive may be a degradation product that forms under the conditions of the leach and is an effective additive in the terms of the invention.
  • the degradation product may be a degradation product of another said additive.
  • the nitrogen-containing complexing agent may include at least two nitrogen atoms.
  • Each of the at least two nitrogen atoms in the additive may be present as a primary amine group, a secondary amine group or a tertiary amine group.
  • the possible interaction of sulfur that has originated from copper minerals in the ores with the at least two nitrogen atoms in the additive may be via the lone pair on each of the nitrogen atoms being involved in pit-dn bonding with the adjacent sulfur atom. Alternatively, this may be via ionic interaction or a combination of both.
  • the nitrogen atoms of the additive are not significantly sterically hindered. Minimising steric hindrance assists the formation of a sufficiently strong interaction (e.g. p ⁇ -d ⁇ bonding, ionic interaction or a combination of both) between the sulfur from the ore and the nitrogen atoms in the additive.
  • the nitrogen-containing complexing agent may include at least two nitrogen atoms spaced by two carbon atoms to permit the additive to form the complex.
  • the additive may be a compound that contains the following molecular scaffold or a polymer that contains the molecular scaffold repeated through the polymer:
  • each nitrogen atom is selected from the group consisting of a primary amine group, a secondary amine group, a tertiary amine group,
  • the carbon atoms may each be substituted or unsubstituted
  • the bonds between the nitrogen atoms and carbon atoms in the scaffold may be single bonds or multiple bonds;
  • the bonds between the two carbon atoms in the scaffold may be single bonds or multiple bonds.
  • Examples of possible additive compound structures include the following:
  • the groups R 1 to R 10 may each be independently selected from the group including alkyl (such as C 1 to C 5 alkyl), alkenyl (such as C 2 to C 5 alkenyl), alkynyl (such as C 2 to C 5 alkynyl), OH, ⁇ O, alkyloxy groups (such as C 1 to C 5 alkyloxy groups), alkenyloxy groups (such as C 2 to C 5 alkynyloxy groups), alkynyloxy groups (such as C 2 to C 5 alkynyloxy groups), C( ⁇ O)R (where R is alkyl, alkenyl or alkynyl), C(O)OH, C(O)OR (where R is alkyl, alkenyl or alkynyl), OC( ⁇ O)R (where R is alkyl, alkenyl or alkynyl), amino, alkylamino (such as C 1 to C 5 alkyl), alkenylamino (such as C 2 to C 5 alky
  • the additive may be a compound of the formula (II) or a polymer formed from two or more monomers of the formula (II):
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may each be independently selected from a lone pair electron, H, alkyl groups (such as C 1 to C 5 alkyl groups), alkenyl groups (such as C 2 to C 5 alkenyl groups), alkynyl groups (such as C 2 to C 5 alkynyl groups), and alkylamino groups (such as C 1 to C 5 alkylamino groups), or the substituents on each of the two nitrogens together form an alkyl or alkynyl group that connect the two nitrogens to form a ring (e.g. the substituents together form a one or two carbon connecting the nitrogens to form a ring);
  • alkyl groups such as C 1 to C 5 alkyl groups
  • alkenyl groups such as C 2 to C 5 alkenyl groups
  • alkynyl groups such as C 2 to C 5 alkynyl groups
  • alkylamino groups such as C 1 to C 5 al
  • R 7 , R 8 , R 9 and R 10 may each be independently selected from H, alkyl (such as C 1 to C 5 alkyl), alkenyl (such as C 2 to C 5 alkenyl), alkynyl (such as C 2 to C 5 alkynyl), OH, alkyloxy groups (such as C 1 to C 5 alkyloxy groups), alkenyloxy groups (such as C 2 to C 5 alkynyloxy groups), alkynyloxy groups (such as C 2 to C 5 alkynyloxy groups), C( ⁇ O)R (where R is alkyl, alkenyl or alkynyl), C(O)OH, C(O)OR (where R is alkyl, alkenyl or alkynyl), OC( ⁇ O)R (where R is alkyl, alkenyl or alkynyl), amino, alkylamino (such as C 1 to C 5 alkyl), alkenylamino (such as C 2 to C 5 al
  • R 1 or R 2 are each independently selected from the groups defined for R1 and R2 above or are connected to another monomer of formula (II).
  • Suitable additives include ethylenediamine, polyethylenimine, imidazole, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminopropane, and 2,3-butanediamine
  • ethylenediamine polyethylenimine
  • imidazole diethylenetriamine
  • triethylenetetramine tetraethylenepentamine
  • 1,2-diaminopropane 1,2-diaminopropane
  • 2,3-butanediamine 2,3-butanediamine
  • the concentration of the additive may be up to 10 g/L, typically up to 5 g/L, typically up to 2.5 g/L, typically up to 1.5 g/L, typically up to 1.25 g/L, and more typically up to 1 g/L, in the leach liquor.
  • the method may include adding the additive to the leach liquor continuously or periodically during the method to maintain a required concentration during the method.
  • the method of addition may be to the ores or concentrates of the ores or tailings of the ores or concentrates prior to leaching.
  • the method for addition may be to agglomerates of ore fragments prior to leaching.
  • the additive may be added while forming agglomerates of ore fragments, as described further below.
  • the method may include adjusting the concentration of the additive in the regenerated leach liquor to maintain the concentration.
  • Leaching may be any suitable option for leaching (a) ore fragments or ore concentrates or tailings of the ores or concentrates or (b) agglomerates of ore fragments or ore concentrates or tailings of the ores or concentrates.
  • leaching may be vat or tank leaching.
  • leaching may be heap leaching agglomerates of ore fragments or ore concentrates or tailings of the ores or concentrates.
  • Leaching may include supplying a leach liquor to a heap of agglomerates from an agglomeration step and allowing the leach liquor to flow through the heap and leach copper from agglomerates and collecting leach liquor from the heap, processing the leach liquor and recovering copper from the liquor.
  • fragment is understood herein to mean any suitable size of mined or treated (e.g. crushed) material having regard to materials handling and processing capabilities of the apparatus used to carry out the method. It is also noted that the term “fragment” as used herein may be understood by some persons skilled in the art to be better described as “particles”. The intention is to use both terms as synonyms.
  • the leach liquor may include microorganisms to assist leaching of copper.
  • the microorganisms may be one or more than one of psychrotolerant or mesophilic or thermophilic (moderate or extreme) bacteria or archaea.
  • the microorganisms may be acidophilic bacteria or archaea.
  • the microorganisms may be thermophilic acidophiles.
  • the leach liquor may contain any suitable chemical oxidants, such as O 2 /SO 2 , pyrolusite, permanganate ions, ferric ions, peroxide ions, and chlorate ions.
  • suitable chemical oxidants such as O 2 /SO 2 , pyrolusite, permanganate ions, ferric ions, peroxide ions, and chlorate ions.
  • Leaching may include controlling the temperature to be less than 100° C., typically less than 85° C., typically less than 75° C., typically less than 65° C., typically less than 60° C., typically less than 55° C., and more typically less than 50° C.
  • Leaching may include controlling the leach temperature to be at least 10° C., typically at least 20° C., typically at least 30° C., typically at least 40° C., and more typically at least 50° C.
  • Leaching may include controlling the oxidation potential of the leach liquor during an active leaching phase of the step to be less than 900 mV, typically less than 850 mV, typically less than 800 mV, typically 500 to 750 mV, more typically in a range of 600 to 750 mV, all potentials being with respect to the standard hydrogen electrode.
  • Leaching and oxidation potential may be assisted by the addition of microorganisms capable of oxidizing ferrous ions, sulfides, polysulfides and sulfur.
  • Leaching may include controlling the pH of the leach liquor to be less than 2.5, typically less than 2.0, typically less than 1.8, and typically less than 1.5.
  • Leaching may include controlling the pH of the leach liquor to be greater than 0.5, typically greater than 1.
  • Leaching may include recovering copper from the leach liquor in downstream copper recovery steps.
  • the leach liquor may be regenerated and recycled to the leach.
  • Leaching may include adjusting the concentration of the additive in the regenerated leach liquor to maintain the concentration.
  • the concentration adjustment may include adding the additive to the regenerated leach liquor to maintain the concentration.
  • the concentration adjustment may include removing the additive from the regenerated leach liquor to maintain the concentration.
  • the method may also include recovering the leached metal as a metal product.
  • this step includes recovering the leached metal from solution in pregnant leach liquor.
  • the advantages of the invention include providing an opportunity for microorganism-assisted and/or chemically assisted leaching of copper minerals in copper-containing ores, particularly low grade ores (i.e. typically less than 2.0 wt. % copper, typically less than 1.5% copper, typically less than 1.0% copper), at relatively low temperatures and at comparatively low operating costs with high recoveries.
  • low grade ores i.e. typically less than 2.0 wt. % copper, typically less than 1.5% copper, typically less than 1.0% copper
  • the method may include an agglomeration step for forming agglomerates of ore fragments for heap leaching.
  • the agglomeration step may include adding the additive during the step.
  • the additive is a polymer-like additive, such as longer chain organic substances, such as polyethylenimine (PEI), it may be preferred to include the additive in agglomerates of ore fragments rather than by adding the additive to the leach liquor.
  • PEI polyethylenimine
  • the agglomeration step may include:
  • the agglomeration step may include forming the PEI solution while ensuring that the solution does not contain constituents that can cause precipitation and/or polymerization of PEI such as ferric ions.
  • the agglomeration step may include mixing together an acid, typically sulfuric acid but could also be dilute hydrochloric, with copper-containing ore fragments, such as fragments containing chalcopyrite.
  • the added acid dose rate may be less than 100 kg H 2 SO 4 /dry t ore, typically less than 50 kg H 2 SO 4 /dry t ore, typically less than 30 kg H 2 SO 4 /dry t ore, and may be less than 10 kg H 2 SO 4 /dry t ore or less than 5 kg H 2 SO 4 /dry t ore.
  • the acid dose rate is 0.5-10 kg H 2 SO 4 /dry t ore.
  • the agglomeration step may include mixing together pregnant leach solution or raffinate with copper-containing ore fragments, such as fragments containing chalcopyrite.
  • the agglomeration step may include mixing microorganisms that can assist leaching with copper-containing ore fragments, such as fragments containing chalcopyrite.
  • the microorganisms may be as described above. Specifically, the microorganisms may be one or more than one of mesophilic, thermophilic (moderate or extreme) or psychrotolerant bacteria or archaea. The microorganisms may be acidophilic bacteria or archaea. The microorganisms may be thermophilic acidophiles.
  • the agglomeration step may include simultaneously mixing and agglomerating fragments.
  • the agglomeration may include mixing fragments in one-step and then agglomerating the mixed fragments in a subsequent step. There may be overlap between the mixing and agglomeration steps.
  • the method may include reducing the size of the mined ore prior to agglomeration.
  • the method may include crushing the mined ore prior to agglomeration.
  • the mined ore may be crushed using any suitable means.
  • the method may include crushing mined ore in a primary crushing step prior to the agglomeration step.
  • primary crushing is understood herein to mean crushing ore to a top size of 250 to 150 mm in the case of copper-containing ores where the copper is in the form of sulfides. It is noted that the top size may be different for ores containing different valuable metals.
  • the method may include crushing mined ore in a primary crushing step and then a secondary and possibly tertiary and possibly quaternary crushing step prior to agglomeration.
  • the invention also provides a heap of material, with the material including the above-described agglomerates.
  • the invention also includes a method of heap leaching that includes:
  • Heap leaching may include recovering copper from the leach liquor in downstream copper recovery steps.
  • the leach liquor may be regenerated and recycled to the heap.
  • the leaching step may include adding the additive during the step.
  • the method may also include recovering the leached metal as a metal product.
  • this step includes recovering the leached metal from solution in pregnant leach liquor.
  • the method may include forming heaps of the copper-containing ores or concentrates.
  • FIG. 1 illustrates the steps in one embodiment of a method of heap leaching agglomerates of fragments of copper-containing ore that contains chalcopyrite and/or enargite with a leach liquor containing an additive in accordance with the present invention
  • FIG. 2 illustrates the enhancement of copper dissolution from relatively pure chalcopyrite mineral grains with the addition of examples of additives in accordance with the invention, with this improvement resulting in copper extraction being higher than the baseline conditions where no additive was added to the test;
  • FIG. 3 illustrates cases where no enhancement of copper dissolution occurred from relatively pure chalcopyrite mineral grains with the addition of samples of additives that do not meet the requirements of the additives in accordance with the invention
  • FIG. 4 illustrates cases where a negative enhancement of copper dissolution occurred from relatively pure chalcopyrite mineral grains with the addition of samples of additives that do not meet the requirements of the additives in accordance with the invention
  • FIG. 5 illustrates the enhancement of copper dissolution from a low copper grade ( ⁇ 1.5 wt. %) ore sample leached at 50° C. with the addition of examples of additives in accordance with the invention, with this improvement resulting in copper extraction being higher than the baseline conditions where no additive was added to the test;
  • FIG. 6 illustrates the enhancement of arsenic dissolution from a low copper grade ( ⁇ 1.5 wt. %) ore sample leached at 50° C. with the addition of examples of additives in accordance with the invention, with this improvement resulting in arsenic extraction being higher than the baseline conditions where no additive was added to the test;
  • FIG. 7 illustrates the enhancement of copper dissolution from a low copper grade ( ⁇ 1.5 wt. %) ore sample leached at 30° C. with the addition of examples of additives in accordance with the invention, with this improvement resulting in copper extraction being higher than the baseline conditions where no additive was added to the test;
  • FIG. 8 illustrates the enhancement of arsenic dissolution from a low copper grade ( ⁇ 1.5 wt. %) ore sample leached at 30° C. with the addition of examples of additives in accordance with the invention, with this improvement resulting in arsenic extraction being higher than the baseline conditions where no additive was added to the test;
  • FIG. 9 is a graph of copper extraction profiles for a chalcopyrite/enargite ore sample leached with and without the addition of the additive polyethylenimine at 50° C.;
  • FIG. 10 is a graph of arsenic extraction profiles for a chalcopyrite/enargite ore sample leached with and without the addition of the additive polyethylenimine at 50° C.
  • the invention extends to heap, vat and tank leaching copper-containing ores that are in the form of fragments or in the form of agglomerates of fragments.
  • the invention also extends to heap, vat, and tank leaching concentrates of copper-containing ores, with the ore concentrates being in any suitable form, including unagglomerated and agglomerated forms.
  • the invention also extends to heap or vat or tank leaching tailings of the ores or concentrates produced for example in flotation or other downstream processing of ores or concentrates.
  • the invention comprises leaching copper-containing ores or concentrates of the ores or tailings of the ores or concentrates with a leach liquor in the presence of an additive that enhances the dissolution of copper from copper minerals in the ores and concentrates by forming a complex between (a) sulfur, that has originated from copper minerals in the ore, and (b) the additive.
  • Nitrogen-containing organic complexing additives are specific examples of the additive.
  • the flow sheet of FIG. 1 shows the steps in one embodiment of a method of heap leaching agglomerates of fragments of copper-containing ore that contains chalcopyrite and/or enargite with a leach liquor containing an additive in accordance with the invention.
  • the method includes the steps of forming agglomerates of copper containing ore in an agglomeration station 3 , forming a heap 5 from the agglomerates, supplying a leach liquor 15 to the heap 5 and taking copper into solution, collecting leach liquor after it has passed through the heap, recovering copper from solution in the leach liquor from the heap in a copper recovery circuit 17 , for example by solvent extraction, and regenerating the leach liquor from the heap and recycling the regenerated leach liquor to the heap.
  • the following feed materials are transferred to the agglomeration station 3 and are mixed together and form agglomerates:
  • the agglomerates produced in the agglomeration station 3 are subsequently used in the construction of the heap 5 .
  • the agglomerates produced in the agglomeration station 3 may be transferred directly to a heap construction site.
  • the agglomerates may be stockpiled and used as required for a heap.
  • the agglomeration station 3 and the heap 5 are typically in close proximity However, this is not essential and may not be the case.
  • the heap may be a heap of the type described in International publication WO2012/031317 in the name of the applicant and the disclosure of the heap construction and leaching process for the heap in the International publication is incorporated herein by cross-reference.
  • copper in the chalcopyrite and other copper-containing minerals in the agglomerates is leached from the agglomerates in the heap 5 via the supply of the leach liquor 15 and is taken into solution in the leach liquor as the leach liquor passes through the heap 5 .
  • the leached copper is recovered from the leach liquor in the downstream copper recovery circuit 17 .
  • the recovered copper 19 is transferred for further processing and the leach liquor 23 is transferred to and regenerated in a regeneration circuit 21 and recycled to the heap 5 as leach liquor 15 to leach more copper from the chalcopyrite and other copper-containing minerals in the agglomerates in the heap 5 .
  • the agglomeration station 3 may be any suitable construction that includes a drum, conveyor (or other device) for mixing the feed materials for the agglomerates and agglomerating the feed materials.
  • the agglomeration conditions in the agglomeration station 3 are selected to form agglomerates of the required size and mechanical properties for the heap 5 .
  • Mixing and agglomerating the feed materials for the agglomerates may occur simultaneously.
  • mixing the feed materials may be carried out first and agglomerating (for example initiated by the addition of the acid) may be carried out after mixing has been completed to a required extent.
  • the timing of adding and then mixing and agglomerating feed materials may be selected to meet the end-use requirements for the agglomerates. For example, it may be preferable in some situations to start mixing fragments containing chalcopyrite and then adding silver in a solution or in a solid form of silver, acid, and microorganisms progressively in that order at different start and finish times in the agglomeration step.
  • the additives of the invention may be added to the leach liquor 15 in the required concentrations.
  • concentration of the additive is up to 10 g/L, up to 5 g/L, up to 2.5 g/L, up to 1.5 g/L, up to 1.25 g/L, or up to 1 g/L, in the leach liquor.
  • the additives of the invention may be added during forming agglomerates in the agglomeration station 3 .
  • the additive is a polymer-like additive, such as longer chain organic substances, such as polyethylenimine (PEI), it may be preferred to add the additive while forming agglomerates in the agglomeration station 3 rather than adding the additive to leach liquor.
  • PEI polyethylenimine
  • the additives tested include ethylenediamine, polyethylenimine, imidazole, bipyridyl, phenanthroline, 8-amineoquinoline, cysteine, glycine, arginine, picoline, putrescine, and spermidine.
  • test work using additive-containing liquor was conducted in small scale leaching reactors.
  • Reactor leaching tests were all conducted at a pH less than 1.8, typically around 1.2.
  • the oxidation potential of the solution was maintained at approximately 700 mV determined with respect to the standard hydrogen electrode to simulate conditions that may be seen when leaching copper ores.
  • the examples in FIGS. 2, 3 and 4 involved the leaching of a chalcopyrite mineral sample containing approximately 90% chalcopyrite mineral, with the remainder being non-reactive gangue minerals.
  • the copper grade in the sample was 29%.
  • the initial leach solution was an acidified iron solution at ⁇ 2 g/L Fe(III) added as a sulfate. These tests were maintained at 50° C. In these methods, additives ethylenediamine, polyethylenimine, and imidazole were tested separately. Specifically, 1 g/L of one of each additive was added to the start of each test.
  • FIG. 2 is a graph that depicts copper extraction profiles (% extraction versus leach days) for chalcopyrite mineral samples leached with leach liquor containing additives ethylenediamine, polyethylenimine, and imidazole.
  • the Figure also includes a copper extraction profile for a baseline test with the same leach liquor without an additive.
  • FIG. 2 shows that there was an improvement observed for the leaching of chalcopyrite minerals with leach liquors in tests with the additives ethylenediamine, polyethylenimine, and imidazole compared to the results in the baseline test.
  • FIG. 3 is a graph that depicts copper extraction profiles for chalcopyrite mineral samples leached with leach liquors in tests with the additives cysteine, glycine, arginine, picoline, putrescine, spermidine, proline and ethanolamine
  • the Figure also includes a copper extraction profile for a baseline test with the same leach liquor without an additive. The Figure shows that there was no improvement observed with the leach liquors containing the additives.
  • FIG. 4 is a graph that depicts copper extraction profiles for chalcopyrite mineral samples leached with leach liquors in tests with additives bipyridyl, phenanthroline, and 8-amineoquinoline.
  • the Figure also includes a copper extraction profile for a baseline test with the same leach liquor without an additive. The Figure shows that there was a negative impact on leaching with the leach liquors containing the additives.
  • FIG. 5 is a graph that depicts copper extraction profiles for a chalcopyrite/enargite ore sample leached with (red squares) and without (blue crosses) the addition of the additive ethylenediamine at 50° C.
  • the Figure also includes a copper extraction profile for the same leach liquor without an additive.
  • FIG. 6 is a graph that depicts arsenic extraction profiles for a chalcopyrite/enargite ore sample leached with (red squares) and without (blue crosses) the addition of the additive ethylenediamine at 50° C.
  • the Figure also includes an arsenic extraction profile for the same leach liquor without an additive.
  • FIG. 7 is a graph that depicts copper extraction profiles for a chalcopyrite/enargite ore sample leached with (green triangles) and without (blue crosses) the addition of the additive ethylenediamine at 30° C.
  • the Figure also includes a copper extraction profile for the same leach liquor without an additive.
  • FIG. 8 is a graph that depicts arsenic extraction profiles for a chalcopyrite/enargite ore sample leached with (green triangles) and without (blue crosses) the addition of the additive ethylenediamine at 30° C.
  • the Figure also includes a copper extraction profile for the same leach liquor without an additive.
  • FIG. 9 is a graph that depicts copper extraction profiles for a chalcopyrite/enargite ore sample leached with (orange circles) and without (blue crosses) the addition of the additive polyethylenimine at 50° C.
  • the Figure also includes a copper extraction profile for the same leach liquor without an additive.
  • FIG. 10 is a graph that depicts arsenic extraction profiles for a chalcopyrite/enargite ore sample leached with (orange circles) and without (blue crosses) the addition of the additive polyethylenimine at 50° C.
  • the Figure also includes an arsenic extraction profile for the same leach liquor without an additive.
  • the successful additives reported above are ethylenediamine, polyethylenimine, and imidazole.
  • the unsuccessful additives reported above are bipyridyl, phenanthroline, 8-amineoquinoline, cysteine, glycine, arginine, picoline, putrescine, spermidine, proline and ethanolamine.
  • additives that make it possible to form complexes comprising (a) sulfur, that has originated from copper minerals in the ore, and (b) additives that can enhance leaching of copper-containing ores or concentrates of the ores.

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