WO2024081705A1 - Compositions de molécules organiques pour la lixiviation de minerai contenant des sulfures métalliques et leurs procédés de préparation et d'utilisation - Google Patents

Compositions de molécules organiques pour la lixiviation de minerai contenant des sulfures métalliques et leurs procédés de préparation et d'utilisation Download PDF

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WO2024081705A1
WO2024081705A1 PCT/US2023/076555 US2023076555W WO2024081705A1 WO 2024081705 A1 WO2024081705 A1 WO 2024081705A1 US 2023076555 W US2023076555 W US 2023076555W WO 2024081705 A1 WO2024081705 A1 WO 2024081705A1
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leaching
cio
group
leaching solution
ore
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PCT/US2023/076555
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Julius Xaver HEIDLAS
Mitchell Louis CATLING
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Basf Se
Basf Corporation
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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
    • 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
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions 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
    • 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
    • C22B3/065—Nitric 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
    • C22B3/06—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
    • C22B3/06—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
    • C22B3/10—Hydrochloric acid, other halogenated 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
    • 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 disclosure relates generally to the field of mining. More particularly, the disclosure relates to compositions for leaching ore and methods of preparation and use thereof.
  • Heap leaching is used to extract precious metals, copper, uranium and other compounds from ore using a series of chemical reactions that assist in the dissolution of specific minerals.
  • the main objective is to increase the rate and total recovery of a target metal from the ore in a typical heap leaching application at ambient temperature.
  • Additives may be added to the leaching composition to help increase wetting and/or dissolution of the ore ultimately releasing more target metal. There is a need for improved leaching compositions to increase recovery of target metals from ore.
  • FTG. 1 shows a schematic diagram of an embodiment of a system for preparing and using a composition for leaching metal-sulfide-containing materials according to embodiments herein.
  • FIG. 2 shows a schematic diagram of a leach column setup used in Example 8.
  • FIG. 3 depicts the results of a leaching a mineral sulfide ore according to embodiments herein.
  • a leaching solution comprising: a leaching additive containing an organic compound with at least one of a sp3 hybridized sulfur or a sulfoxide; and a lixiviant.
  • the leaching additive comprises one or more compound of Formula (A) or Formula (B):
  • Ci Cio linear or branched alkyl group which may be interrupted by one or more functional groups
  • Ci Ci to C io hydroxy alkyl group, a ether thereof or an ester thereof;
  • Ci Cio aminoalkyl group or a nitrogen functionalized derivative thereof
  • Ci Ci to Cio carboxyalkyl; an amino acid residue having the structure -(CnH2n)CH(NH2)COOH where n is an integer between 0 and 6;
  • Ci Cio alkenyl group
  • Ci Cio alkynyl group
  • a carbonyl group having the structure -C( O)R 3 ;
  • Ci Ci to Cio alkoxy group
  • Ci Ci to Cio alkynyloxy group
  • Cio Cio dialkenylamino or a sulfide group having the formula -S-R 4 , wherein R 3 and R 4 is each, independently, H, OH, NH2, Ci to Cio linear or branched alkyl group which may be interrupted by one or more functional groups, Ci to Cio hydroxyalkyl group, a ether thereof or an ester thereof, Ci to Cio aminoalkyl group or a nitrogen functionalized derivative thereof, Ci to Cio carboxyalkyl, an amino acid residue, C2 to Cio alkenyl group, C2 to Cio alkynyl group, a carbonyl group, Ci to Cio alkoxy group, C2 to Cio alkenyloxy group, C2to Cio alkynyloxy group, C2 to Cio alkenylamino group, C2 to Cio dialkenylamino, or a sulfide group, optionally, wherein Formula (A) or Formula (B) is cyclic.
  • the leaching solution and/or leaching additive does not contain one or more of thiocarbonyl functionality or group, sulfonic acid functionality or group and/or an alkyl bridged polyamine.
  • the leaching solution and/or leaching additive is free of one or more of thiourea, ethylene thiourea, formamidine disulfide, a sulfonamide, methane sulfonic acid, ethylenediamine, polyethylenimine, imidazole, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminopropane, 2,3-butanediamine, or combinations thereof.
  • the one or more leaching additive of Formula (A) or Formula (B) is cyclic.
  • An example of a cyclic leaching additive is thioxane.
  • the leaching solution can have a pH of less than about 4, less than about 3, less than about 2, or less than about 1, or about 0.1 to about 4.0, or about 1 to about
  • the leaching additive may be present in an amount of about 0.001 mM to about 67 mM, 0. 1 mM to about 2 mM, or any individual value or sub-range within these ranges, based on the total volume of the leaching solution.
  • the lixiviant comprises an acid. Suitable acids include, but are not limited to, sulfuric acid, hydrochloric acid, nitric acid, or combinations thereof. [0012] In some embodiments, the leaching solution further includes an oxidant. Suitable oxidants include, but are not limited to, one or more of a ferric ion, hydrogen peroxide, a nitrate anion, sodium chlorate, or combinations thereof.
  • the leaching solution further includes an iron oxidizing bacterium and/or a sulfur oxidizing bacterium.
  • Iron oxidizing bacterium includes, for example, thiobacillus ferrooxidans, acidithiobacillus ferrooxidans or combinations thereof.
  • Sulfur oxidizing bacterium includes, for example, sulfobacillus disulfidooxidans.
  • the leaching solution further includes an ore comprising metal- sulfide species.
  • the ore may be in the form of a plurality of particles, a plurality of agglomerates, a concentrate, a matte, or combinations thereof.
  • the ore is a copper-bearing ore containing sulfide species.
  • the copper-bearing ore can include chalcopyrite (CuFeS2), bornite (Cu5FeS 4 ), enargite (Cu 3 AsS 4 ), tetrahedrite (Cui2Sb4Si 3 ), tennantite (Cui2As4Si 3 ), covellite (CuS), chalcocite (C S), copper sulfide of the formula Cu x S y wherein an atomic ratio of x:y is about 1 to about 2, carrolite (CUC02S4), or combinations thereof.
  • the ore is a non-copper bearing ore comprising sulfide species.
  • the non-copper bearing ore can include, but is not limited to, millenite (NiS), pentlandite (FegNigSie), molybdenite (M0S2), violarite (FebfoS-i), cobaltite (CoAsS), pyrite (FeS ), linnaeite (C03S4), sphalerite ((Zn,Fe)S), cattierite (C0S2), or combinations thereof.
  • the leaching solution further includes metal values.
  • metal values include, but are not limited to, at least one of copper, cobalt, nickel, zinc, molybdenum, vanadium and/or iron.
  • Such methods can include leaching the ore (e.g., by in-situ leaching, heap leaching, percolation leaching, and/or agitation/tank leaching) with a leaching solution containing an organic molecule having at least one of a sp3 hybridized sulfur and/or a sulfoxide according to embodiments described herein to form a pregnant leaching solution.
  • the methods include extracting metal values from the pregnant leaching solution using a solvent extraction process, wherein the solvent extraction process forms a metal-rich organic stream.
  • Embodiments of methods further include recovering metal values from the metalrich organic stream, optionally wherein recovering metal values is by an electrowinning process.
  • the metal values comprise copper, and the method provides a copper recovery from chalcopyrite ore of about 95 wt% to about 99 wt%, or any individual value or subrange within this range, in 200 days when performed at 22 degrees Celsius at atmospheric pressure; or a copper recovery from chalcopyrite ore of about 99 wt% in about 75 days, or any individual value or sub-range within this range, when performed at 22 degrees Celsius at atmospheric pressure.
  • the method further includes preparing a concentrate of the ore containing metal-sulfides using a flotation technique prior to leaching. In some embodiments, the methods further include preparing a concentrate of metal sulfide ore using a smelter process to produce a matte prior to leaching. In one or more embodiment, the matte is a nickel-copper matte or a lead-zinc matte.
  • the present disclosure relates generally to the field of mining and more specifically, to leaching a target metal such as copper from one or more of the following sources of ore: (1) metal - sulfide ore, (2) ore concentrate, (3) leaching residue, (4) a matte, and/or (5) tailings produced by upstream processing of ore, for example, magnetic separation or flotation.
  • a target metal such as copper from one or more of the following sources of ore: (1) metal - sulfide ore, (2) ore concentrate, (3) leaching residue, (4) a matte, and/or (5) tailings produced by upstream processing of ore, for example, magnetic separation or flotation.
  • the term “matte” as used herein refers to the product of a smelter, for example, a crude mixture of molten sulfides formed as an intermediate product of the smelting of sulfide ores of metals.
  • the “matte” contains a metal (e.g., copper, nickel, lead) and
  • copper ores are usually smelted to matte, for example, containing 40-45 percent copper along with iron and sulfur, which is then treated by converting in a Bessemer-type converter. Air is blown into the molten matte, oxidizing the sulfur to sulfur dioxide and the iron to iron oxide that combines with a silica flux to form slag, leaving the copper in the metallic state.
  • Smelting of nickel sulfide ores yields a matte in which nickel and copper make up about 15 percent, iron about 50 percent, and sulfur the remainder; the iron is removed in a converting furnace, and the sulfides of copper and nickel are separated before being reduced to the metals.
  • Smelting of lead sulfide ores produces a liquid layer of copper sulfide matte that can be decanted, along with slag and speiss, from the lead bullion.
  • the disclosure relates to the addition of a chemical additive comprising of an organic sp3 hybridized sulfur and/or sulfoxide to increase the rate of dissolution of a base metal from the sulfidic ore, such as copper from chalcopyrite (CuFeS2). Redistribution of the energy of orbitals of individual atoms to give orbitals of equivalent energy happens when two atomic orbitals combine to form a hybrid orbital in a molecule. This process is called hybridization. During the process of hybridization, the atomic orbitals of comparable energies are combined together and the process typically involves the merging of an ‘s’ orbital with ‘p’ orbitals or alternatively an ‘s’ orbital with ‘d’ orbitals.
  • a chemical additive comprising of an organic sp3 hybridized sulfur and/or sulfoxide to increase the rate of dissolution of a base metal from the sulfidic ore, such as copper from chalcopyrite (CuFeS2). Redistribution of the energy of orbitals of individual atoms
  • Hybrid orbitals are useful in explaining atomic bonding properties and molecular geometry.
  • Methane gas (CH4) is a good example to consider for hybridization theory.
  • the carbon atom forms four (4) single bonds wherein the valence-shell s orbital combines with three (3) valence-shell p orbitals. This combination leads to the formation of four (4) equivalent sp3 hybrid orbitals. These will have a tetrahedral arrangement around the carbon atom, which is bonded via these hybrid orbitals to four (4) different hydrogen atoms.
  • sp3 hybridization refers to a molecule containing one ‘s’ orbital and three (3) ‘p’ orbitals belonging to the same shell of an atom, that have combined together to form four (4) equivalent orbitals, referred to as tetrahedral hybridization.
  • the new orbitals formed are called sp3 hybrid (or hybridized) orbitals.
  • Each sp3 hybrid orbital has 25% s character and 75% p character.
  • Additional examples of molecules containing sp3 hybridized orbitals include the carbon atoms in ethane (C2H6) and chloromethane (CH3Q), and both the carbon and sulfur atoms in dimethyl sulfide (CH3SCH3).
  • Base metal containing ores are typically classified into two categories — oxi die and sulfidic ores.
  • Oxi die ores e.g., cuprite, malachite, and azurite
  • Oxi die ores are generally found near the surface as they are often the oxidation products of the typically deeper primary and secondary sulfidic ores or have formed in areas where metals have leached from the surface in aqueous solution, becoming trapped and concentrated in the host formation.
  • Sulfidic ore deposits e.g., chalcopyrite, bornite, and chalcocite
  • Sulfidic ores are generally sub-divided into two groups, primary and secondary. Primary sulfidic ores are generally in the initial state whereas secondary sulfidic ores have undergone some subsequent weathering and oxidation processes.
  • mines typically process the ore to extract and concentrate the target valuable metal(s) through either a selective flotation or hydrometallurgical process.
  • Selective flotation most commonly used for sulfidic ores, requires the ore to be finely ground to liberate individual grains of metal containing mineral from the waste (gangue) material.
  • the ground ore is processed as an aqueous slurry, with the addition of surfaceactive chemicals which facilitate the flotation and separation of the metal containing sulfide minerals from the gangue.
  • the recovered metal sulfide minerals can then be further processed to recover the metal(s), often by pyrometallurgical processing.
  • the ore is treated with a lixiviant which dissolves the target valuable metal(s) into aqueous solution, leaving the waste (gangue) material in the solid phase.
  • the aqueous solution containing the solubilized metal(s) is collected and separated from the gangue material and the metal(s) can then be recovered in a more concentrated form by one or more processes such as precipitation and/or solvent extraction.
  • Leaching is typically accomplished by applying an aqueous solution containing a lixiviant to a collection of the ore and/or a concentrate.
  • a common lixiviant is sulfuric acid (“H2SO4”) because it provides efficient and cost-effective liberation of the metal from the ore.
  • the leaching process can be an in-situ, heap, dump, percolation, and/or agitation leaching process.
  • the intrinsic principles of leaching are the same, the process: 1) can dissolve the ore minerals rapidly enough to make commercial extraction possible and the lixiviant shows chemical inertness toward the gangue minerals because in situations where gangue minerals are attacked, an excessive amount of the lixiviant is consumed and the leach liquor will be fouled with impurities to an undesirable extent; 2) are cheap and readily obtainable in large quantities; and 3) can be regenerated in the subsequent processes following leaching.
  • the underpinning characteristic of leaching is that regardless of the lixiviant used, it interacts with the ore particles in a way that allows for transfer of the desired metal from the ore into a collected and then managed solution.
  • Heap leaching is a common method of leaching in hydrometallurgical processes.
  • metal-containing material is piled into a heap and wetted with a solution of lixiviant, significant time is required for the solution to percolate down through the heap before it can be collected and supplied to subsequent operations.
  • the extraction process can require several days to months.
  • the leaching of metal bearing ore typically requires the use of a solution such as an acid, a base and/or an oxidant (e.g., a ferric ion) to facilitate recovery target metals (e.g., copper) into a lixiviant.
  • a solution such as an acid, a base and/or an oxidant (e.g., a ferric ion) to facilitate recovery target metals (e.g., copper) into a lixiviant.
  • oxidant e.g., a ferric ion
  • target metals e.g., copper
  • This process is commonly applied for oxide minerals of metal-bearing ores, where the target metal is subsequently recovered from the lixiviant by means of solvent extraction/electrowinning (SX/EW), direct electrowinning, cementation, and/or precipitation reactions to create a salable metal product.
  • SX/EW solvent extraction/electrowinning
  • a group of chemical additives that can be added to the lixiviant in the leaching process to (a) increase the rate of dissolution of metal sulfide ores and/or mattes and (b) enhance the oxidation and dissolution of metal sulfide ores past the point of passivation commonly seen under standard leaching conditions.
  • passivation refers to oxidizing or protecting the sulfide surface of an ore from water and oxygen.
  • the additives described were selected in part due to their chemistry being compatible with downstream processes such as SX/EW or direct electrowinning.
  • compositions, methods of preparation and methods of use thereof can improve the leaching efficiency of a target metal during an ore leaching process.
  • the leaching of some ore minerals e.g., primary and secondary sulfide minerals
  • diffusion of the oxidant to the surface of the mineral ore can increase the leaching efficiency.
  • copper sulfide ores such as chalcopyrite are the most abundant naturally occurring copper mineral, estimated to account for about 70% of the copper deposits found in the earth’s crust, but are difficult to leach with conventional methods (e.g., using sulfuric acid).
  • compositions and methods described herein increase the recovery of target metals (e.g. copper) from ores (e.g., primary and/or secondary sulfide ores) through the utilization of an additive having at least one organic molecule with a sp3 hybridized sulfur and/or sulfoxide in combination with a lixiviant. This combination increases the leaching efficiency of the ore at ambient temperature.
  • target metals e.g. copper
  • ores e.g., primary and/or secondary sulfide ores
  • an additive having at least one organic molecule with a sp3 hybridized sulfur and/or sulfoxide in combination with a lixiviant. This combination increases the leaching efficiency of the ore at ambient temperature.
  • the target metal values include copper, and methods as described herein provide a copper recovery from chalcopyrite of about 50 wt% to about 100 wt%, about 75 wt% to about 99.9 wt%, about 90 wt% to about 99 wt%, or any individual value or sub-range therein, under standard temperature and pressure conditions (e.g., 20-25°C, 1.0 atm).
  • compositions and methods as described herein include a chemical additive (e.g., a leaching aid) to a lixiviant (e.g., an acid) used to recover a target metal (e.g., copper) from a mined ore containing metal-sulfide species (e.g., chalcopyrite, that is, CuFeS2).
  • a chemical additive e.g., a leaching aid
  • a lixiviant e.g., an acid
  • a target metal e.g., copper
  • the chemical additive includes at least one organic sp3 hybridized sulfur atom and/or a sulfoxide group, and a wide variety of such molecules have been identified as being suitable in the disclosed compositions and methods.
  • suitable chemical additives include, but are not limited to, cystine, cysteine, cysteamine, dimethyl-sulfoxide, methionine, or combinations thereof.
  • Chemical additives according to embodiments herein can enhance and increase the rate of metal recovery from sulfide ores. This is of great advantage to the mine as it helps increase the yields from existing heaps and leach residue and avoids processes such as flotation and/or smelting to recover valuable metals from sulfide ores.
  • the addition of a chemical additive containing at least one organic molecule having a sp3 hybridized sulfur and/or sulfoxide in small concentrations to a hydrometallurgical leaching process can increase the rate of dissolution of target metals from sulfidic ores, concentrates, tailings, and leach residues, and enhance the oxidation and total dissolution that is achieved relative to similar leaching conditions conducted in the absence of the chemical additive.
  • compositions and methods described herein relate to the leaching of metal-sulfide containing ores, ore concentrate, leaching residue, or tailings produced by upstream processing of ore such as magnetic separation or flotation.
  • methods described herein relate to recovery of a least one target metal from an ore, ore concentrate, leach residue, matte, and/or mine tailings containing at least one metal sulfide, such as, but not limited to, chalcopyrite. This recovery can be completed in acidic conditions with a solution pH of ⁇ 4.0.
  • the mechanism of action relates to the use of a sp3 hybridized sulfur (i.e., the orbital structure around an atom of sulfur in a molecule) and/or to a sulfoxide such that the resulting molecule(s) is(are) designed to be soluble in raffinate.
  • Improved molecules also feature another functional group that can function as a Lewis base to facilitate the coordination of a metal in the sulfide matrix such as an imine, carbonyl, amine, pyridine, azole, etc.
  • a leaching solution that includes a leaching additive containing an organic compound having a sp3 hybridized sulfur and/or in combination with a lixiviant.
  • the leaching additive comprises one or more compound of Formula (A) or Formula (B):
  • Ci Cio linear or branched alkyl group which may be interrupted by one or more functional groups
  • Ci Cio hydroxyalkyl group, a ether thereof or an ester thereof;
  • Ci Cio aminoalkyl group or a nitrogen functionalized derivative thereof
  • Ci Ci to C 10 carboxyalkyl; an amino acid residue having the structure -(CnH2n)CH(NH2)COOH where n is an integer between 0 and 6 - this structure may have straight and/or branched alkyl groups;
  • Ci Ci to Cio alkoxy group
  • R 1 to R 3 is each, independently, selected from the groups defined for R 1 and R 2 above with respect to Formulas (A) and (B).
  • R 1 or R 2 is H. In certain embodiments, only one or only two of R 1 , R 2 , R 3 or R 4 is H. In some embodiments, when R 1 is H, R 2 is not H or when R 2 is H, R 1 is not H. In some embodiments, Formulas (A) and (B) meet the proviso that when either R 1 and R 2 is H, then R 1 and R 2 are not the same.
  • the linear or branched Ci to C10 alkyl group can include or be interrupted with one or more functional group (e.g., ethers, esters, amides, carboxyls).
  • R 1 when R 1 is methyl, R 2 is not H or methyl or when R 2 is methyl, R 2 is not H or methyl.
  • R 1 when R 1 is methyl, R 2 is a C4 alkyl optionally substituted with one or more amine and/or carboxyl group.
  • the Ci to C10 hydroxyalkyl group can include, but is not limited to, methylol and/or 2-hydroxyethyl or ethers and/or esters thereof.
  • the Ci to C 10 aminoalkyl group can include, but is not limited to, aminomethyl and/or 2-aminoethyl and optionally can include nitrogen functionalized derivatives thereof such as N-alkylaminoalkyl.
  • the Ci to C10 carboxyalkyl group can include, but is not limited to, carboxymethyl and/or 2-carboxy ethyl or common derivatives such as esters and amides thereof.
  • the amino acid residue can include any chemical method of adjoining an alpha- (a-), beta- (0-), gamma- (y-) or delta- (8-) amino acid.
  • the Ci to C10 hydroxyalkyl group can include, but is not limited to methylol and/or 2-hydroxyethyl.
  • the sulfide groups S-R 4 where R 4 is defined as R 1 or R 2 set forth above can include, but is not limited to, the alkyl groups, alkenyl groups, alkynyl groups and/or carbonyl groups.
  • the leaching solution and/or leaching additive does not comprise one or more of thiocarbonyl functionality or group, sulfonic acid functionality or group and/or an alkyl bridged polyamine.
  • the leaching solution and/or leaching additive is free of one or more of thiourea, ethylene thiourea, formamidine disulfide, a sulfonamide, methane sulfonic acid, ethylenediamine, polyethylenimine, imidazole, diethylenetriamine, tri ethylenetetramine, tetraethylenepentamine, 1,2-diaminopropane, 2,3 -butanediamine, or combinations thereof.
  • the leaching additive is a sp3 hybridized sulfur and/or sulfoxide containing organic molecule.
  • the leaching additive may be present in an amount of about 0.001 mM to about 67 mM, 0.1 mM to about 2 mM, or any individual value or sub-range within these ranges, based on the total volume of the leaching solution.
  • the leaching solution includes metal values. Suitable metal values include, but are not limited to, at least one of copper, cobalt, nickel, zinc, molybdenum, vanadium, iron, or combinations thereof.
  • Leaching solutions according to embodiments herein may have a pH of less than about 4, less than about 3, less than about 2, less than about 1, about 0.1 to about 4.0, about 1 to about 2.5, or any individual value or sub-range within these ranges.
  • the lixiviant can comprise an acid, such as, sulfuric acid, nitric acid, or combinations thereof.
  • the leaching solution further includes an oxidant. Suitable oxidants include, but are not limited to, a ferric ion, hydrogen peroxide, a nitrate anion, sodium chlorate, or combinations thereof.
  • the leaching solution may include at least one of an iron oxidizing bacterium (e.g., thiobacillus ferrooxidans, acidithiobacillus ferrooxidans) or a sulfur oxidizing bacterium (e.g., sulfobacillus disulfidooxidans).
  • an iron oxidizing bacterium e.g., thiobacillus ferrooxidans, acidithiobacillus ferrooxidans
  • a sulfur oxidizing bacterium e.g., sulfobacillus disulfidooxidans.
  • One or more iron oxidizing bacterium may be included to convert ferrous ions to ferric ion during the leaching process.
  • One or more sulfur oxidizing bacterium may be included to convert elemental sulfur produced during leaching to sulfate in the generation of acid.
  • these bacterium are present on the surface of the ore as it resides in its natural environment.
  • the leaching solution may contain ore-derived bacteria as a result at a concentration of less than about 1000 ppm.
  • the bacterium from an external source may be added to the leaching solution, for example, at a concentration of greater than 1000 ppm.
  • Bacterium from an external source may be added to a leaching solution to inoculate various species and assist in the leaching process.
  • the leaching solution further includes a metal sulfide ore.
  • the metal sulfide ore may be in the form of at least one of a plurality of particles, a plurality of agglomerates, a concentrate, a matte, or combinations thereof.
  • the metal sulfide ore is a copper-bearing sulfide ore.
  • Suitable copper-bearing sulfide ore includes, but is not limited to, chalcopyrite (CuFeS2), bornite (CusFeS4), enargite (CU3ASS4), tetrahedrite (Cui2Sb 4 Si 3 ), tennantite (Q112AS4S13), covellite (CuS), chalcocite (C S), carrolite (CUC02S4), or combinations thereof.
  • the metal sulfide ore is a non-copper bearing sulfide ore.
  • Suitable non-copper bearing sulfide ore includes, but is not limited to, one or more of millenite (NiS), pentlandite (FegNigSie), molybdenite (M0S2), violarite (FeNi2S4), cobaltite (CoAsS), pyrite (FeS2), linnaeite (C03S4), sphalerite ((Zn,Fe)S), cattierite (C0S2), or combinations thereof.
  • the methods include combining one or more leaching additives (e.g., comprising a sp3 hybridized sulfur and/or a sulfoxide) with a lixiviant to form the leaching solution.
  • the one or more leaching additives can be added at a concentration of about 0.001 mM to about 67 mM, 0.1 mM to about 2 mM, or any individual value or sub-range within these ranges, based on the total volume of the leaching solution.
  • Methods according to embodiments herein can include adding one or more leaching additives as described herein to a leach liquor from a mining process.
  • the method may further include adjusting the concentration of the one or more leaching additives in the leach liquor to maintain a concentration of up to about 10 g/L, up to about 5 g/L, up to about 2.5 g/L, up to about 1.5 g/L, up to about 0.5 g/L, or up to about 0.01 g/L, or any individual value or sub-range within these ranges, in the leach liquor at about 0.05 mM to about 70 mM, about 0.5mM to 1 mM, or any individual value or sub-range within these ranges.
  • the methods include adjusting the pH of the leaching solution to less than about 4, less than about 3, less than about 2, less than about 1, about 0.1 to about 4.0, about 1 to about 2.5, or any individual value or sub-range within these ranges.
  • adjusting includes adding lixiviant in a greater amount and/or at various concentrations.
  • the lixiviant can comprise an acid, such as, sulfuric acid, nitric acid, or combinations thereof.
  • the method includes adding an oxidant to the leaching solution.
  • Suitable oxidants include, but are not limited to, one or more of a ferric ion, hydrogen peroxide, a nitrate anion, sodium chlorate, or combinations thereof.
  • the methods can include adding (e.g., from an external source) an iron oxidizing bacterium (e.g., thiobacillus ferrooxidans, acidithiobacillus ferrooxidans) and/or a sulfur oxidizing bacterium (e.g., sulfobacilhis disulfidooxidans) leach liquor or leaching solution.
  • an iron oxidizing bacterium e.g., thiobacillus ferrooxidans, acidithiobacillus ferrooxidans
  • a sulfur oxidizing bacterium e.g., sulfobacilhis disulfidooxidans
  • leach liquor or leaching solution e.g., leaching liquor or leaching solution.
  • iron oxidizing bacterium e.g., thiobacillus ferrooxidans, acidithiobacillus ferrooxidans
  • a sulfur oxidizing bacterium e.g., sulfobacilhis disul
  • the method includes combining a metal sulfide ore with the leaching solution.
  • the metal sulfide ore may be in the form of a plurality of particles, a plurality of agglomerates, a concentrate, a matte, or combinations thereof.
  • the metal sulfide ore is a copper-bearing sulfide ore.
  • Suitable copper-bearing sulfide ore includes, but is not limited to, chalcopyrite (CuFeS2), bornite (CusFeS ⁇ , enargite (CU3ASS4), tetrahedrite (Cui2Sb 4 Si3), tennantite (CU12AS4S13), covellite (CuS), chalcocite (C S), carrolite (CUC02S4), or combinations thereof.
  • the metal sulfide ore is a non-copper bearing sulfide ore.
  • Suitable non-copper bearing sulfide ore includes, but is not limited to, millenite (NiS), pentlandite (FegbfeSie), molybdenite (M0S2), violarite (FeNiiS ), cobaltite (CoAsS), pyrite (FeS2), linnaeite (C03S4), sphalerite ((Zn,Fe)S), cattierite (C0S2), or combinations thereof.
  • FIG. 1 shows a schematic diagram of an embodiment of a leaching system 100 suitable for forming and using compositions according to embodiments herein to leach a metal -containing material.
  • a leaching solution comprising one or more leaching additives according to embodiments herein and extracting one or more target metals at a higher concentration than in a solution that does not contain the described leaching additives.
  • the methods described herein can be applied to leaching applications such as, but not limited to, in-situ, heap/percolation leaching, and/or vat/tank leaching.
  • the ore may contain a variety of particle size fragments. In some cases, the ore may be agglomerated prior to beginning the leaching process.
  • a concentrate of metal-sulfide ore may be prepared by flotation techniques prior to leaching.
  • a concentrate of metal sulfide ore may be prepared as a result of a smelter process to produce a matte, such as a nickel-copper or lead-zinc matte prior to leaching.
  • methods of recovering metal values from a metal sulfide ore include leaching the metal sulfide ore with a leaching solution containing an organic molecule with a sp3 hybridized sulfur and/or sulfoxide according to form a pregnant leaching solution.
  • the methods further include extracting metal values from the pregnant leaching solution using a solvent extraction process, wherein the solvent extraction process forms a metal-rich organic stream; and recovering metal values from the metal-rich organic stream (e.g., using an electrowinning process).
  • Metal values can include copper, cobalt, nickel, zinc, molybdenum, vanadium, iron, or combinations thereof.
  • the lixiviant includes sulfuric acid.
  • the metal values include copper, wherein the method provides an improved copper recovery from chalcopyrite ore at atmospheric temperature and pressure as compared to a method of leaching ore with a leaching solution that does not contain organic additives according to embodiments herein.
  • “Agitation Testing” or “stirred jar test” experiments in the presence of leaching additives according to embodiments herein and a comparative additive were conducted in triplicate. All volumes and masses were measured to within 1% of the indicated amount. Mineral samples were crushed and sieved down to less than the required size for the experiment. The respective leaching additives according to embodiments herein and where tested, the comparative additive was dosed into the lixiviant solution at the required concentration for the respective tests. Each translucent “wide mouth” 500 mL polypropylene bottle was charged with the required amount of mineral and 400mL of lixiviant solution containing the respective additive at the listed concentration. The fill line was marked on each bottle using a permanent marker. Each bottle was fitted with a standard 1.5-inch polypropylene disk impeller and lid with a central 1 cm hole which leaves an air gap between the impeller shaft and the lid.
  • Example 1 Agitation Testing to extract Copper from Chalcopyrite Mineral
  • Test Temperature All tests were conducted at 25°C in a water bath.
  • Test Temperature All tests were conducted at 23°C in a water bath.
  • Test Temperature All tests were conducted at 23°C in a water bath.
  • Additive 2 was the only product screened that was found to increase the total recovered amount of copper significantly relative to the control.
  • Additive 2 was tested at a range of dosages according to Test Procedure I using the following conditions:
  • Test Temperature All tests were conducted at 25°C in a water bath.
  • Example 5 Agitation Testing to extract Metal from different Mineral Species
  • Additive 2 was tested according to Test Procedure 1 using the following conditions:
  • NisS2 2 g ⁇ 45 pm sieved NisS2 sourced from Sigma Aldrich with 73.3% Ni
  • Test Temperature All tests were conducted at 25°C in a water bath.
  • Example 6 Agitation Testing to extract Copper from Chalcopyrite in the Presence of 35 g/L Chloride in Addition to Additive 2
  • Additive 2 was tested according to Test Procedure 1 using the following conditions:
  • Test Temperature All tests were conducted at 25°C in a water bath.
  • Additive 2 was tested according to Test Procedure 1 using the following conditions:
  • Test Temperature All tests were conducted at 25°C in a water bath.
  • a raffinate leach solution with the following characteristics: 2.66 g/L Fe, 0.85 g/L H2SO4, ORP of 506mV (IM Ag/AgCl) and a pH of 1.79 was used to leach a sulfide rich ore in column testing in a laboratory.
  • the ore used was from a copper mill flotation feed and had a total copper grade of 1.2%, with 96.2% of the copper present as sulfide minerals, (of which 92.5% was chalcopyrite) and 3.8% as acid soluble minerals.
  • the irrigation rate was set at 1 L/hr/m 2 and the ore was agglomerated with 26.8 kg/ton sulfuric acid prior to column loading, which equated to 100% acid consumption of the ore.
  • An weight of 4 kg of ore were used per column, and the test was conducted in duplicate using the setup described in FIG. 2 and the results averaged.
  • the mass, density, pH, and metallurgical data of the PLS were collected and reviewed. The results of this testing are shown in FIG. 3.
  • the same raffinate was used for each test.
  • the columns were irrigated with the same raffinate described above that had been dosed with 100 mg/L of Additive 2 prior to irrigation starting.
  • FIG. 3 shows that with the presence of Additive 2 in the lixiviant, copper extraction from the primary sulfide rich ore has continued on a linear trajectory over the period of testing (about 9 months) and has far exceeded the expected theoretical passivation limit of chalcopyrite of about 25%. This demonstrates that the additive is effective in promoting the oxidation of the copper beyond what would be expected under standard sulfuric acid leaching conditions at room temperature.
  • an iron oxidizing bacterium includes a single bacterium as well as a plurality of bacteria.
  • the term “about” in connection with a measured quantity refers to the normal variations in that measured quantity as expected by one of ordinary skill in the art in making the measurement and exercising a level of care commensurate with the objective of measurement and the precision of the measuring equipment.
  • the term “about” includes the recited number ⁇ 10%, such that “about 10” would include from 9 to 11.
  • the term “at least about” in connection with a measured quantity refers to the normal variations in the measured quantity, as expected by one of ordinary skill in the art in making the measurement and exercising a level of care commensurate with the objective of measurement and precisions of the measuring equipment and any quantities higher than that.
  • the term “at least about” includes the recited number minus 10% and any quantity that is higher such that “at least about 10” would include 9 and anything greater than 9. This term can also be expressed as “about 10 or more.”
  • the term “less than about” typically includes the recited number plus 10% and any quantity that is lower such that “less than about 10” would include 11 and anything less than 11.
  • Weight percent if not otherwise indicated, is based on an entire composition free of any volatiles, that is, based on dry solids content.
  • the term “combinations thereof’ refers to an operable mixture or grouping of any two or more elements preceding the term.
  • “A, B, C, or combinations thereof’ refers to “A and B,” “B and C,” “A and C” and “A, B and C.”

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Abstract

L'invention concerne des solutions de lixiviation comprenant un additif de lixiviation ayant au moins un composé organique ayant un soufre hybridé sp3 et/ou un sulfoxyde ; et un lixiviant. L'invention concerne également des procédés de préparation et d'utilisation de ceux-ci.
PCT/US2023/076555 2022-10-14 2023-10-11 Compositions de molécules organiques pour la lixiviation de minerai contenant des sulfures métalliques et leurs procédés de préparation et d'utilisation WO2024081705A1 (fr)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
US5413624A (en) * 1991-02-22 1995-05-09 Mbx Systems, Inc. Enhancement of bioleach systems using nutrient additives
US6767522B1 (en) * 1998-07-30 2004-07-27 Hahn-Meitner-Institut Berlin Gmbh Method for leaching sulfide-containing materials with microorganisms and use of sulphur-containing amino acids in leaching with microorganisms
WO2014201507A1 (fr) * 2013-06-21 2014-12-24 Technological Resources Pty. Limited Dérivés de lactone homosérine pour améliorer l'extraction des éléments minéraux pendant l'extraction biologique de minerais

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Publication number Priority date Publication date Assignee Title
US5413624A (en) * 1991-02-22 1995-05-09 Mbx Systems, Inc. Enhancement of bioleach systems using nutrient additives
US6767522B1 (en) * 1998-07-30 2004-07-27 Hahn-Meitner-Institut Berlin Gmbh Method for leaching sulfide-containing materials with microorganisms and use of sulphur-containing amino acids in leaching with microorganisms
WO2014201507A1 (fr) * 2013-06-21 2014-12-24 Technological Resources Pty. Limited Dérivés de lactone homosérine pour améliorer l'extraction des éléments minéraux pendant l'extraction biologique de minerais

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PEKSA ANNA ET AL: "Amino acid composition of flesh-coloured potatoes as affected by storage conditions", FOOD CHEMISTRY, ELSEVIER LTD, NL, vol. 266, 7 June 2018 (2018-06-07), pages 335 - 342, XP085418269, ISSN: 0308-8146, DOI: 10.1016/J.FOODCHEM.2018.06.026 *

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