Systems and methods of material extraction from sulfidic minerals

Abstract

A copper metal (Cu0) product is recovered from a copper concentrate such as chalcopyrite (CuFeS2) via oxidative leaching with a cerium (Ce(IV)) redox couple. Ce4+ having a concentration between about 0.1 M and about 0.5 M is contacted with chalcopyrite which results in leaching of a copper-containing product. Electrowinning copper metal from the copper-containing product via electrochemical processes can also regenerate spent chemical oxidizers for reuse in recovery of additional copper. The yield of these processes can be further enhanced by treatment of the copper concentrate with acids, ferric iron, and drying agents such as blown gases, acetone, etc. Previous attempts to chemically recover copper from chalcopyrite, e.g., with vanadium reducing agents (V(II)), have suffered from slow reaction kinetics, low yields, toxic intermediates or byproducts, etc. Cerium is less expensive than V(II), and its use minimizes toxic H2S generation, reducing overall costs while increasing yields.

Description

Attorney Docket No.: 104820-201 SYSTEMS AND METHODS OF MATERIAL EXTRACTION FROM SULFIDIC MINERALS CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application Nos.63 / 651,100, filed May 23, 2024, and 63 / 468,592, filed May 24, 2023, which are incorporated by reference as if disclosed herein in their entireties. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT

[0002] This invention was made with U.S. Government support under Grant Number DE- AR0001340 awarded by the Department of Energy. The United States Government has certain rights in the invention. BACKGROUND

[0003] Copper is an important mineral resource with global demand rising alongside the expansion of renewable energy technologies that rely on it. Chalcopyrite (CuFeS2), the most abundant source of copper accounting for 70-80% of the world's supply, can be subjected to a variety of pyrometallurgical processes for copper extraction. However, these traditional pyrometallurgical processes are typically energy-intensive and pollutive. Because of the environmental impact of the exhaust emanating from a smelter, U.S.-mined chalcopyrite concentrate is often shipped to countries with less stringent regulations.

[0004] Alternative approaches such as hydrometallurgy can be more cost-effective and minimize environmental impacts, but often are slow with low yield. Further, many sulfidic minerals are refractory without costly reagents. Recent advances in hydrometallurgy rely on oxidative or reductive leaching of copper-containing products, but these use costly reagents and careful handling of high-risk intermediates. By way of example, a technology was developed that utilizes a vanadium redox couple for hydrometallurgical processing of CuFeS2 via reductive leaching of the copper. However, there are two disadvantages associated with this reductive leaching technology: vanadium is costly, and the process produces H2S as an intermediate. The wide adoption of the reductive leaching of the copper means an acceptance of the risk of treating an H2S intermediate.Attorney Docket No.: 104820-201

[0005] The deployment of hydrometallurgy for the oxidative leaching of chalcopyrite has been attempted for decades with minimal success, at least in part due to passivation of CuFeS2. Agreement on the structure and composition of the passivation layer remains elusive, but it is widely agreed that the room temperature oxidative leaching of CuFeS2is too slow to be economical, although high-temperature, high pressure leaching processes have been developed. Leach rates achievable via oxidative leaching of CuFeS2 using a V(V) / V(IV) redox couple were only 50-60% of copper after 35 days.

[0006] What is desired, therefore, are hydrometallurgical processes utilizing advanced electrochemical technologies that recycle redox reagents, enabling safe, efficient copper extraction. SUMMARY

[0007] Aspects of the present disclosure are directed to a method of producing a copper product. In some embodiments, the method includes providing a composition including copper concentrate; contacting the copper concentrate with a solution including one or more chemical oxidizers; oxidizing at least a portion of the copper within the copper concentrate via reaction with the chemical oxidizer; isolating a copper-containing product from the composition; and isolating a copper metal product from the copper-containing product. In some embodiments, oxidizing at least a portion of the copper within the copper concentrate via reaction with the chemical oxidizer occurs at about room temperature. In some embodiments, the one or more chemical oxidizers includes Ce(IV). In some embodiments, the concentration of Ce(IV) in the solution is between about 0.1 M and about 0.5 M. In some embodiments, the copper concentrate includes chalcopyrite.

[0008] In some embodiments, the step of isolating a copper metal product from the copper- containing product includes electrowinning copper metal from the copper-containing product. In some embodiments, the step of isolating a copper metal product from the copper-containing product includes isolating a liquid phase reaction product from the composition, the liquid phase reaction product including concentrations of a reduced chemical oxidizer, a concentration of ferric iron ions; and cupric ions; feeding the liquid phase reaction product to an electrochemical device including a cathode compartment and an anode compartment; applying an electrical potential across the electrochemical device; producing a concentration of ferrous iron ions in the cathode compartment; producing a concentration of recycled chemical oxidizer in the anode compartment; and contacting at least a portion of the recycled chemical oxidizer with the composition. In some embodiments, the method includes removing an effluent stream from theAttorney Docket No.: 104820-201 cathode compartment, wherein the effluent stream includes a concentration of the ferrous iron ions and a concentration of reduced chemical oxidizer; isolating a ferrous iron product from the effluent stream to form a reduced chemical oxidizer stream; and returning the reduced chemical oxidizer stream to the anode compartment. In some embodiments, the method includes one or more steps of drying the composition.

[0009] In some embodiments, contacting the copper concentrate with a solution including one or more chemical oxidizers includes contacting the copper concentrate with a concentration of ferric iron ions; contacting the copper concentrate with a second solution including a concentration of acid, or combinations thereof. In some embodiments, the concentration of the acid is between about 0.1 M and about 1.0 M; the concentration of ferric iron ions is between about 0.3 M and about 0.5 M; or combinations thereof. In some embodiments, the acid component includes H2SO4.

[0010] Aspects of the present disclosure are directed to a system for producing a copper metal product from a copper concentrate. In some embodiments, the system includes a source of copper concentrate; an oxidation reactor in communication with the source of copper concentrate, the oxidation reactor including a solution including one or more chemical oxidizers; a copper-containing product outlet stream in fluid communication with the oxidation reactor; and an electrowinning reactor in fluid communication with the copper-containing product stream, the electrowinning reactor producing a copper product and a recycled chemical oxidizer stream in fluid communication with the oxidation reactor. In some embodiments, the one or more chemical oxidizers includes Ce(IV). In some embodiments, the copper concentrate includes chalcopyrite. In some embodiments, the system includes one or more separators. In some embodiments, the electrowinning reactor includes a cathode compartment and an anode compartment; an effluent stream in fluid communication with the cathode compartment and the separator, the effluent stream including a concentration of ferric iron ions and reduced chemical oxidizer; a recycled chemical oxidizer stream in fluid communication with the separator and the anode compartment. In some embodiments, the concentration of Ce(IV) in the solution is between about 0.1 M and about 0.5 M.

[0011] In some embodiments, the system includes an acid inlet stream in fluid communication with the oxidation reactor; a ferric iron ion inlet stream in fluid communication with the oxidation reactor; one or more drying agents in fluid communication with the oxidation reactor, or combinations thereof. In some embodiments, the drying agent includes a source of acetone; aAttorney Docket No.: 104820-201 source of gas, wherein the gas includes air, nitrogen, or combinations thereof; a heat source; a source of ethanol, or combinations thereof.

[0012] Aspects of the present disclosure are directed to a method of producing a copper metal product, providing a composition including copper concentrate including contacting the composition with a first solution to form a treated composition, the first solution including a concentration of ferric iron ions, one or more acids, or combinations thereof; drying the treated composition with one or more drying agents; reacting the treated composition with one or more chemical oxidizers in a first instance to oxidize at least a portion of the copper of the treated composition and form a reacted composition; drying the reacted composition with one or more drying agents; reacting the reacted composition with one or more chemical oxidizers in at least a second instance to oxidize at least a portion of the copper of the reacted composition; isolating from the reacted composition a copper-containing product stream including a concentration of cupric ions; electrowinning a copper product from the copper-containing product and forming a recycled chemical oxidizer stream; and contacting the recycled chemical oxidizer stream with the treated composition.

[0013] In some embodiments, the copper concentrate includes chalcopyrite and the one or more chemical oxidizers includes Ce(IV). In some embodiments, the concentration of Ce(IV) is between about 0.1 M and about 0.5 M. In some embodiments, the drying agent includes a source of acetone; a source of gas, wherein the gas includes air, nitrogen, or combinations thereof; a heat source; a source of ethanol, or combinations thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The drawings show embodiments of the disclosed subject matter for the purpose of illustrating the invention. However, it should be understood that the present application is not limited to the precise arrangements and instrumentalities shown in the drawings, wherein:

[0015] FIG 1 is a chart of a method of producing a metal product according to some embodiments of the present disclosure;

[0016] FIG.2 is a graph showing percentage of copper leached from a metal concentrate using systems and methods according to some embodiments of the present disclosure;

[0017] FIG.3 is a graph showing x-ray diffraction (XRD) analysis results for metal concentrates after oxidative leaching according to some embodiments of the present disclosure;Attorney Docket No.: 104820-201

[0018] FIG.4 is a chart of a method producing a metal product according to some embodiments of the present disclosure;

[0019] FIG.5A includes schematic representations of a plurality of systems for oxidative leaching of metal concentrates according to some embodiments of the present disclosure;

[0020] FIG.5B is a graph showing percentage of copper leaching from a metal concentrate by the exemplary systems portrayed in FIG.5A; and

[0021] FIG.6 is a schematic representation of a system of producing a target metal product from a metal concentrate according to some embodiments of the present disclosure. DETAILED DESCRIPTION

[0022] Referring now to FIG.1, some embodiments of the present disclosure are directed to a method 100 of producing a metal product. In some embodiments, the metal product is composed at least substantially of copper metal. In some embodiments, at 102, a composition is provided. In some embodiments, the composition includes a mixture of solids. In some embodiments, the composition includes one or more copper concentrates. As used herein, the term “copper concentrate” refers to a medium including a concentration of copper, the extraction of which is desired. In some embodiments, the copper concentrate is a copper-containing mineral or combination of copper-containing minerals. In some embodiments, the composition is naturally occurring, man-made, or combinations thereof. In some embodiments, the copper concentrate is naturally occurring, man-made, or combinations thereof. In some embodiments, the copper concentrate includes chalcopyrite. The embodiments of the present disclosure will discuss treatment of copper concentrations for the purpose of obtaining a copper product. However, the present disclosure is not intended to be limiting in this regard, as one of ordinary skill in the art would understand that embodiments of the present disclosure may also be applied to concentrates including non-copper components, and may be utilized for the isolation of non- copper products as well. In some embodiments, the composition is provided 102 to a suitable reaction vessel including one or more inputs and one or more outputs for facilitating introduction and extraction of reactants and products to facilitate production of the copper product, as will be discussed in greater detail below.

[0023] At 104, at least a portion of the composition, e.g., the copper concentrate, is contacted with a solution including one or more chemical oxidizers. In some embodiments, the chemical oxidizer is configured to oxidize copper within the composition. In some embodiments, the chemical oxidizer is configured to oxidize copper within the copper concentrate. In someAttorney Docket No.: 104820-201 embodiments, the chemical oxidizer is configured to be regenerated following reduction via one or more electrochemical processes, as will be discussed in greater detail below. In some embodiments, the chemical oxidizers include oxidizing ions, a compound including oxidizing ions, or combinations thereof. In some embodiments, the chemical oxidizers include cerium (IV) or “Ce(IV)”, e.g., Ce(IV) ions, compounds including Ce(IV), or combinations thereof. Ce(IV) is a strong oxidizing agent that advantageously can be regenerated at large scales. Further, its solubility depending on pH and temperature enables it to be exploited for process integration. In some embodiments, the concentration of Ce(IV) in the solution contacted 104 with the composition is between about 0.1 M and about 0.5 M. In some embodiments, the concentration of Ce(IV) in the solution contacted 104 with the composition is 0.5 M. In some embodiments, the solution is contacted 104 with the composition for about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11 hours, about 12 hours, about 13 hours, about 14 hours, about 15 hours, about 16 hours, about 17 hours, about 18 hours, about 19 hours, about 20 hours, about 21 hours, about 22 hours, about 23 hours, about 1 day, about 2 days, about 3 days, about 4 days, about 5 days, at least 6 days, etc. At 106, at least a portion of the copper present in the composition, e.g., within the copper concentrate, is oxidized via reaction with the chemical oxidizer. In some embodiments, at least steps 104 and 106 occur at about room temperature. In some embodiments, at least steps 104 and 106 occur at about standard temperature and pressure.

[0024] In an exemplary embodiment of the present disclosure, an amount of chalcopyrite isoxidized 106 according to Reactions 1 and 2 below:(Reaction 1)CuFeS2 + 5Ce4+ → Cu2+ + Fe3+ + 2S0 + 5Ce3+ (Reaction 2)In the exemplary embodiment utilizing chalcopyrite as a copper concentrate, oxidation of copper at step 106 converts a concentration of Cu(I) as present in chalcopyrite to a concentration of Cu(II), causing the oxidized copper to leach out of the concentrate and into the solution. Ferric iron ions leach out of the chalcopyrite into the solution as well. Advantageously, neither Reaction 1 nor Reaction 2 generate any H2S, a toxic chemical evolved during other hydrometallurgical processes that must be mitigated, increasing the complexity and cost of those processes. A series of compositions were treated with chemical oxidizers consistent with embodiments of the present disclosure in an effort to identify the amount of oxidizer, e.g., Ce(IV), to leach copper from various loadings of copper concentrates. The results areAttorney Docket No.: 104820-201 provided in Table 1 below. As can be seen, in these exemplary embodiments, for every mole of chalcopyrite leached, about 9.4 moles of Ce(IV) were consumed. Time Leached1 hour 4 hours 24 hoursConcentrate Loaded8 g / L 16 g / L 24 g / L 4 g / L 8 g / L 16 g / L 4 g / L 8 g / L 16 g / Lmoles Ce4+ consumed Moles8.81 8.88 9.66 9.59 9.20 9.91 9.62 9.38 9.15CuFeS2 Table 1: Results showing leaching of copper from copper concentrates consistent with embodiments of the present disclosure

[0025] Referring now to FIG.2, the capabilities of chemical oxidizers to leach copper from copper concentrates consistent with embodiments of the present disclosure was demonstrated. In as little as 4 hours, nearly 70% of the copper had been leached, that number rising to about 80% by the end of 1 day. The amount of Ce(IV) to obtain the same mole production of metal leachate was found to decrease over time. Referring now to FIG.3, the solid products after leaching were determined using x-ray diffraction (XRD) analysis. Even after leaching the majority of the metal content from the chalcopyrite consistent with embodiments of the present disclosure, most of the solids that remained were CuFeS2. No passivation layer could be detected.

[0026] Referring again to FIG.1, in some embodiments, the composition is also contacted with one or more additional solutions, e.g., a second solution. In some embodiments, the additional solution includes one or more acids, a concentration of ferric iron ions, or combinations thereof. Treatment with dilute concentrations of acid was found to reduce the amount of Ce(IV) used to obtain equivalent mole amounts of copper leachate. In some embodiments, the concentration of the acid contacted with the composition is between about 0.1 M and about 1.0 M. In some embodiments, the acid includes H2SO4. In some embodiments, the concentration of ferric iron ions contacted with the composition is between about 0.3 M and about 0.5 M. In some embodiments, method 100 includes one or more steps of drying the composition, which will be discussed in greater detail below.

[0027] At 108, a copper-containing product is isolated from the composition. The copper- containing product can be isolated by any suitable process, e.g., filtration, decanting, etc., or combinations thereof. In some embodiments, the copper-containing product is a liquid includingAttorney Docket No.: 104820-201 leachate from the composition. In some embodiments, the copper-containing product includes concentrations of copper ions, e.g., Cu2+, iron ions, e.g., Fe3+, reduced chemical oxidizers, e.g., Ce(III), or combinations thereof. In some embodiments, isolating 108 includes isolating a liquid phase reaction product from the composition. In some embodiments, the liquid phase reaction product includes concentrations of a reduced chemical oxidizer, a concentration of ferric iron ions, and cupric ions. At 110, a copper metal product is isolated from the copper-containing product.

[0028] In some embodiments, the copper metal product is isolated 110 via an electrowinning process. In some embodiments, the copper metal product is isolated 110 by feeding at least a portion of the copper-containing product, e.g., the liquid phase reaction product / leachate from the copper concentrate, to one or more electrochemical devices. In some embodiments, the electrochemical device includes at least one pair of electrodes, e.g., a cathode and an anode, in electrical communication via one or more electrolytes, and a power supply configured to apply an electrical potential across the devices, e.g., the electrodes. In some embodiments, the cathode is positioned within a cathode compartment in the electrochemical device. In some embodiments, the cathode is in contact with one or more catholytes. In some embodiments, the anode is positioned within an anode compartment in the electrochemical device. In some embodiments, the anode is in contact with one or more anolytes.

[0029] In some embodiments, the copper-containing product, e.g., liquid phase reaction product, that is fed to the electrochemical device is fed substantially evenly to the cathode compartment and the anode compartment. In some embodiments, an electrical potential is applied across the electrochemical device. As the electrical potential is applied to the electrochemical device, in some embodiments, a concentration of the reduced chemical oxidizer, e.g., Ce(III), in the anode compartment is oxidized, e.g., back to Ce(IV) as a recycled chemical oxidizer. In some embodiments, at 112, at least a portion of the recycled chemical oxidizer is contacted with the composition.

[0030] Further, as the electrical potential is applied to the electrochemical device, in some embodiments, copper in the copper-containing product is reduced to copper metal, Cu0, in the cathode compartment, which can be recovered as a copper product, e.g., at step 110. In some embodiments, ferric iron ions are converted to ferrous iron ions in the cathode compartment. In some embodiments, an effluent stream is then removed from the cathode compartment. In some embodiments, this effluent stream includes a concentration of the ferrous iron ions and a concentration of reduced chemical oxidizer (present in the copper-containing product provided toAttorney Docket No.: 104820-201 the cathode compartment). In some embodiments, a ferrous iron product is isolated from the effluent stream, thus forming a reduced chemical oxidizer stream. This reduced chemical oxidizer stream can then be returned to the anode compartment where is oxidized back to recycled chemical oxidizer, e.g., for contacting with the composition at step 112.

[0031] Referring now to FIG.4, some embodiments of the present disclosure are directed to a method 400 of producing a metal product, e.g., a copper metal product. As discussed above, at 402, a composition is provided. In some embodiments, the composition includes a mixture of solids. In some embodiments, the composition includes one or more copper concentrates. In some embodiments, the copper concentrate includes chalcopyrite. At 404, at least a portion of the composition is contacted with a first solution to form a treated composition. As discussed above, in some embodiments, the first solution includes a concentration of ferric iron ions, one or more acids, or combinations thereof.

[0032] In some embodiments, at 406, the treated composition is dried with one or more drying agents. In some embodiments, the drying agent includes a source of acetone, a source of gas, a heat source, a source of ethanol, or combinations thereof. In some embodiments, the gas includes air, nitrogen, or combinations thereof. In some embodiments, the gas is blown over the medium to be dried, e.g., the treated composition, to increase the rate at which the medium is dried.

[0033] At 408, the treated composition is reacted with one or more chemical oxidizers in at least a first instance. As discussed above, in some embodiments, the one or more chemical oxidizers includes Ce(IV). In some embodiments, the concentration of Ce(IV) is between about 0.1 M and about 0.5 M. At least a portion of the copper in the treated composition is oxidized by the chemical oxidizers, forming a reacted composition. In some embodiments, at 410, the reacted composition is dried with one or more drying agents, e.g., consistent with step 406 above.

[0034] Referring now to FIGs.5A-5B, drying the composition, e.g., the treated composition, the reacted composition, etc., has been demonstrated to increase the percentage of target metal leached from the composition. Exemplary embodiments of the present disclosure were prepared that incorporated pretreatment with ferric iron ions and acid, as well as one or two drying steps. These exemplary embodiments were compared to other exemplary embodiments that did not include a drying step. A single drying step increased the concentration of copper leached from the concentrate compared with the control embodiments, with the embodiment having an additional drying step recovering yet more copper.Attorney Docket No.: 104820-201

[0035] Referring again to FIG.4, in some embodiments, at 412, the reacted composition is reacted with one or more chemical oxidizers in at least a second instance. As in step 408, another portion of the metal, e.g., copper, this time in the reacted composition, is oxidized by the chemical oxidizers. In some embodiments, at least one additional drying step and / or reaction step is performed, consistent with the description of steps 406, 408, 410, and 412 above.

[0036] At 414, a copper-containing product stream is isolated from the reacted composition. As discussed above, in some embodiments, the copper-containing product stream includes a concentration of cupric ions. In some embodiments, at 416, a copper product is electrowinned from the copper-containing product. In some embodiments, electrowinning 416 also oxidizes chemical oxidizers reduced in the creation of the metal-containing product stream, e.g., at steps 408 and 412, forming recycled chemical oxidizer. In some embodiments at, 420, a recycled chemical oxidizer stream is formed and subsequently contacted with the treated composition, reacted composition, or combinations thereof.

[0037] Referring now to FIG.6, some embodiments of the present disclosure are directed to a system 600 for producing a target metal product from a metal concentrate, e.g., a copper metal product from a copper concentrate. In some embodiments, system 600 includes an oxidation reactor 602. Oxidation reactor 602 includes a solution 604. As discussed above, in some embodiments, one or more chemical oxidizers. In some embodiments, the one or more chemical oxidizers includes Ce(IV). In some embodiments, the concentration of Ce(IV) is between about 0.1 M and about 0.5 M. In some embodiments, oxidation reactor 602 is two or more reactors arranged in series, parallel, or combinations thereof, e.g., for facilitating a series of methods steps such as steps, 406, 408, 410, and 412 discussed above.

[0038] In some embodiments, oxidation reactor 602 is in communication with a source 606 of copper concentrate. As discussed above, in some embodiments, the copper concentrate includes chalcopyrite. In some embodiments, system 600 includes a source 608 of one or more acids. In some embodiments, system 600 includes an acid inlet stream 608A in fluid communication with oxidation reactor 602, copper concentrate source 606, or combinations thereof. In some embodiments, system 600 includes a source 610 of ferric iron ions. In some embodiments, system 600 includes a ferric iron ion inlet stream 610A in fluid communication with oxidation reactor 602, copper concentrate source 606, or combinations thereof. In some embodiments, system 600 includes a source 612 of one or more drying agents. In some embodiments, drying agents 612 are in fluid communication with oxidation reactor 602, metal concentrate source 606,Attorney Docket No.: 104820-201 or combinations thereof. As discussed above, in some embodiments, the drying agent includes a source of acetone, a source of gas, a heat source, a source of ethanol, or combinations thereof.

[0039] In some embodiments, system 600 includes a copper-containing product outlet stream 614. As discussed above, in some embodiments, copper-containing product outlet stream 614 includes a concentration of a copper-containing product. In some embodiments, copper-containing product outlet stream 614 is in fluid communication with oxidation reactor 602, e.g., to remove the copper-containing product and other components, such as ferric iron ions, reduced chemical oxidizer, or combinations thereof, from the reactor.

[0040] In some embodiments, system 600 includes an electrowinning reactor 616. In some embodiments, electrowinning reactor 616 includes an anode compartment 616A and a cathode compartment 616B. In some embodiments, electrowinning reactor 616 is in fluid communication with copper-containing product stream 614. In some embodiments, copper- containing product stream 614 flows from oxidation reactor 602 and is split substantially evenly between anode compartment 616A and cathode compartment 616B. In some embodiments, electrowinning reactor 616 includes a power supply 616P.

[0041] As discussed above, as an electric potential is applied across the electrodes (not pictured) of electrowinning reactor 616, reduced chemical oxidizer is oxidized in anode compartment 616A to recycled chemical oxidizer. A stream 618 including recycled chemical oxidizer can then be recycled, e.g., to oxidation reactor 602. Further, copper in cathode compartment 616B is reduced to copper metal, which can be recovered as a product 620. Ferric iron irons in cathode compartment 616B can be reduced as well. In some embodiments, an effluent stream 622 is removed from electrowinning reactor 616, containing at least concentrations of ferrous iron ions and reduced chemical oxidizer. In some embodiments, system 600 includes one or more separators 624. Separators 624 are configured to remove ferrous iron ions from effluent stream 622. In some embodiments, system 600 includes a recycled chemical oxidizer stream 626 in fluid communication with separator 624 and anode compartment 616A, thus returning reduced chemical oxidizer to electrowinning reactor 616 for oxidation, recovery, and recycling back to oxidizing reactor 602 in stream 618.

[0042] Systems and methods of the present disclosure advantageously utilize oxidative leaching of copper-containing products and copper metal from chalcopyrite via a cerium redox couple. Previous attempts to chemically recover copper from chalcopyrite have suffered from myriad drawbacks, including costly reactants, slow reaction kinetics, low yields, toxic intermediates or byproducts, etc. The hydrometallurgical methods for oxidative copper extraction consistent withAttorney Docket No.: 104820-201 embodiments of the present disclosure combat these issues. The systems and methods of the present disclosure can be more cost-effective than previous reductive leaching processes. Cerium is less expensive relative to other leachants such as vanadium reducing agents, e.g., V(II), and its use minimizes toxic gas generation, such as H2S, the effective mitigation of which results in additional processing and resources. Further, useful concentrations of copper products are recovered in mere hours of processing time, and the chemical oxidizers can be electrochemically recycled to reduce materials costs. Finally, the processes of the present disclosure advantageously include acid, ferric iron, and drying agent treatments of copper concentrates to further increase copper-containing product yield when used in combination with the Ce(IV) oxidizers.

[0043] Although the invention has been described and illustrated with respect to exemplary embodiments thereof, it should be understood by those skilled in the art that the foregoing and various other changes, omissions and additions may be made therein and thereto, without parting from the spirit and scope of the present invention.

Claims

Attorney Docket No.: 104820-201 CLAIMS What is claimed is:

1. A method of producing a copper product, comprising: providing a composition including copper concentrate; contacting the copper concentrate with a solution including one or more chemical oxidizers; oxidizing at least a portion of the copper within the copper concentrate via reaction with the chemical oxidizer; isolating a copper-containing product from the composition; and isolating a copper metal product from the copper-containing product, wherein the one or more chemical oxidizers includes Ce(IV).

2. The method according to claim 1, wherein the copper concentrate includes chalcopyrite.

3. The method according to claim 1, wherein the step of isolating a copper metal product from the copper-containing product includes: electrowinning copper metal from the copper-containing product.

4. The method according to claim 3, wherein the step of isolating a copper metal product from the copper-containing product includes: isolating a liquid phase reaction product from the composition, the liquid phase reaction product including concentrations of: a reduced chemical oxidizer; a concentration of ferric iron ions; and cupric ions, feeding the liquid phase reaction product to an electrochemical device including a cathode compartment and an anode compartment; applying an electrical potential across the electrochemical device;Attorney Docket No.: 104820-201 producing a concentration of ferrous iron ions in the cathode compartment; producing a concentration of recycled chemical oxidizer in the anode compartment; and contacting at least a portion of the recycled chemical oxidizer with the composition.

5. The method according to claim 4, further comprising: removing an effluent stream from the cathode compartment, wherein the effluent stream includes a concentration of the ferrous iron ions and a concentration of reduced chemical oxidizer; isolating a ferrous iron product from the effluent stream to form a reduced chemical oxidizer stream; and returning the reduced chemical oxidizer stream to the anode compartment.

6. The method according to claim 1, wherein the concentration of Ce(IV) in the solution is between about 0.1 M and about 0.5 M.

7. The method according to claim 1, further comprising one or more steps of drying the composition.

8. The method according to claim 1, wherein contacting the copper concentrate with a solution including one or more chemical oxidizers includes: contacting the copper concentrate with a concentration of ferric iron ions; contacting the copper concentrate with a second solution including a concentration of acid, or combinations thereof.

9. The method according to claim 8, wherein: the concentration of the acid is between about 0.1 M and about 1.0 M; the concentration of ferric iron ions is between about 0.3 M and about 0.5 M, or combinations thereof.Attorney Docket No.: 104820-201 10. The method according to claim 9, wherein the acid component includes H2SO4.

11. The method according to claim 1, wherein oxidizing at least a portion of the copper within the copper concentrate via reaction with the chemical oxidizer occurs at about room temperature.

12. A system for producing a copper metal product from a copper concentrate, the system comprising: a source of copper concentrate; an oxidation reactor in communication with the source of copper concentrate, the oxidation reactor including a solution including one or more chemical oxidizers; a copper-containing product outlet stream in fluid communication with the oxidation reactor; and an electrowinning reactor in fluid communication with the copper-containing product stream, the electrowinning reactor producing a copper product and a recycled chemical oxidizer stream in fluid communication with the oxidation reactor, wherein the one or more chemical oxidizers includes Ce(IV).

13. The system according to claim 12, wherein the copper concentrate includes chalcopyrite.

14. The system according to claim 12, further comprising: an acid inlet stream in fluid communication with the oxidation reactor; a ferric iron ion inlet stream in fluid communication with the oxidation reactor; one or more drying agents in fluid communication with the oxidation reactor, or combinations thereof.

15. The system according to claim 14, wherein the drying agent includes: a source of acetone; a source of gas, wherein the gas includes air, nitrogen, or combinations thereof;Attorney Docket No.: 104820-201 a heat source; a source of ethanol, or combinations thereof.

16. The system according to claim 12, further comprising one or more separators, and wherein the electrowinning reactor includes: a cathode compartment and an anode compartment; an effluent stream in fluid communication with the cathode compartment and the separator, the effluent stream including a concentration of ferric iron ions and reduced chemical oxidizer; a recycled chemical oxidizer stream in fluid communication with the separator and the anode compartment.

17. The system according to claim 12, wherein the concentration of Ce(IV) in the solution is between about 0.1 M and about 0.5 M.

18. A method of producing a copper metal product, comprising: providing a composition including copper concentrate; contacting the composition with a first solution to form a treated composition, the first solution including a concentration of ferric iron ions, one or more acids, or combinations thereof; drying the treated composition with one or more drying agents; reacting the treated composition with one or more chemical oxidizers in a first instance to oxidize at least a portion of the copper of the treated composition and form a reacted composition; drying the reacted composition with one or more drying agents; reacting the reacted composition with one or more chemical oxidizers in at least a second instance to oxidize at least a portion of the copper of the reacted composition;Attorney Docket No.: 104820-201 isolating from the reacted composition a copper-containing product stream including a concentration of cupric ions; electrowinning a copper product from the copper-containing product and forming a recycled chemical oxidizer stream; and contacting the recycled chemical oxidizer stream with the treated composition, wherein the copper concentrate includes chalcopyrite and the one or more chemical oxidizers includes Ce(IV).

19. The method according to claim 18, wherein the drying agent includes: a source of acetone; a source of gas, wherein the gas includes air, nitrogen, or combinations thereof; a heat source; a source of ethanol, or combinations thereof.

20. The method according to claim 19, wherein the concentration of Ce(IV) is between about 0.1 M and about 0.5 M.

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