Ore resetting process for copper leaching

Abstract

Methods, compositions and systems are provided that improve recovery of copper from previously leached copper ores. A reset solution comprising a chelating agent and a reducing agent is provided to a heap of previously leached and passivated ore to improve copper recovery kinetics in subsequent leaching stages.

Claims

1. A method to improve recovery of copper from copper ore-containing material, comprising: providing a heap of copper ore previously leached; performing a reset step, wherein the heap of copper ore previously leached is irrigated with a reset solution comprising a chelating agent and a reducing agent; and performing a leaching step, wherein the irrigated heap from the reset step is further treated with a leaching solution comprising acid and a leaching agent to obtain a copper-enriched Pregnant Leaching Solution (PLS); and wherein said method further comprises a conditioning step, prior to performing the reset step, wherein the heap is irrigated with a conditioning solution having a pH in a range of 3.5 to 14.

2. The method according to claim 1, wherein said conditioning solution comprises a buffering agent.

3. The method according to claim 2, wherein said buffering agent in the conditioning solution is selected from the group consisting of citric acid, lactic acid, tartaric acid, ascorbic acid, salicylic acid, tetrasodium glutamate diacetate acid, ethylenediaminetetraacetic acid, pyruvic acid, succinic acid, aspartic acid, gallic acid, fumaric acid, malic acid, their conjugate bases, and a mixture thereof.

4. The method according to claim 3, wherein the buffering agent in the conditioning solution is in a concentration of above 50 mM.

5. The method according to claim 4, wherein the conditioning step is conducted up to the point in which the heap reaches a pH of at least 2.

6. The method according to claim 1, wherein the conditioning solution contains less than 0.1 mM of a reducing agent.

7. The method according to claim 1, wherein the conditioning, the reset and the leaching steps are cyclically repeated.

8. The method according to claim 1, wherein said copper ore provided comprises copper oxides, primary copper sulfides, secondary copper sulfides, or a mixture thereof.

9. The method according to claim 1, wherein said ore provided is primarily chalcopyrite.

10. The method according to claim 1, wherein said reset solution used in the reset step has a redox potential in a range of 200 to 700 mV and a pH in a range 2 to 6.

11. The method according to claim 1, wherein said chelating agent in the reset solution is selected from the group consisting of citric acid, lactic acid, tartaric acid, ascorbic acid, salicylic acid, tetrasodium glutamate diacetate acid, ethylenediaminetetraacetic acid, pyruvic acid, succinic acid, aspartic acid, gallic acid, fumaric acid, malic acid, gluconic acid, their conjugate bases, or a mixture thereof.

12. The method according to claim 1, wherein said reducing agent in the reset solution is a reagent selected from the group consisting of bisulfite ion, dithionite ion, metabisulfite ion, and a mixture thereof.

13. The method according to claim 1, wherein a ratio of said chelating agent and said reducing agent in the reset solution on a molar basis, is between 4:1 to 1:100.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) In order for the present invention to be better understood and for its practical applications to be appreciated, the following Figures are provided and referenced hereinafter. It should be noted that the Figures are given as examples only and in no way limit the scope of the invention. Like components are denoted by reference numerals.

(2) FIG. 1 schematically depicts an overview of the process according to embodiments of the invention.

(3) FIG. 2, FIG. 3 and FIG. 4 plot the solubilization of iron species from passivated ore, according to various embodiments of the invention, including comparative examples.

(4) FIG. 5 depicts copper recovery versus time, showing the effect of the reset process on copper recovery according to an embodiment of the invention.

(5) FIG. 6 is a detail of FIG. 5, depicting operational parameters (redox potential and pH conditions) using the resetting process according to an embodiment of the invention.

(6) FIG. 7A, FIG. 7B, FIG. 7C, FIG. 7D, FIGS. 7E and 7F depict the effect of the reset solution on the surface of the passivated ore by means of scanning electron microscopy with energy dispersive X-ray spectroscopy spectral analyses (SEM-EDS).

(7) FIG. 8A and FIG. 8B depicts the effect of the reset solution on the surface of the passivate ore, by means of sulfur removal determined by X-ray photoelectron spectroscopy (XPS)

DETAILED DESCRIPTION OF THE INVENTION

(8) The following detailed description is provided to facilitate comprehension of the invention. However, it should be noted that the invention can be practiced without specific details. In other instances, known methods, procedures, components, modules, units, and/or circuits have not been described in detail so as to avoid obscuring the invention.

(9) The disclosure herein pertains to a method that is performed on a heap of copper ore that has undergone prior leaching. This method is applied prior to a subsequent leaching process. It may be applicable for the recovery of copper from copper oxide ores, copper sulfide ores, including copper sulfide species that are rich in chalcopyrite, as well other sulfide species, such as enargite and bornite, and/or secondary copper sulfide ores, such as chalcocite-digenite and covellite. The term copper ore is understood broadly to refer to ore containing material and may refer to ore that has been previously agglomerated and cured, or un-treated such as mine tailings, run-of mine (ROM), crushed ore or native ore that has not been leached. As used herein inputs broadly refers to any reagent, ore-containing material or other process component conveyed to a process stage, however the component is conveyed.

(10) In embodiments, copper ore is defined as primarily copper sulfide if the copper-containing species in the native ore comprise more than 50% by weight of primary and secondary copper sulfide species. Likewise, an ore is considered primarily chalcopyrite if more than 50% of the copper is contained in chalcopyrite. It should be noted that any native ore typically comprises more than one species of copper mineral.

(11) The term heap is used to describe any material containing copper ore at any stage of the process, following stacking. A heap may be defined as a pile or stack of crushed ore, often agglomerated with acid. For example, a heap may have a flat top surface area of 0.1-1 km.sup.2, and a height of 7 m. It should be noted, however, that these dimensions are merely indicative and do not limit the invention in any way. A heap may be modelled using one or more columns of copper ore-containing material in order to approximate reaction times and kinetics. Therefore, as used herein, the term heap encompasses such a column. Additionally, a heap may also refer to Run-of-Mine (ROM) material stacked on a leach pad without prior crushing and agglomeration.

(12) The term irrigation rate is the volume applied of solution which may be reset solution or leaching solution applied over a specific area of the heap during a period of time and the area refers to the surface are at the top of the heap, or in the case of a column, an equivalent area. It is given in units of L/h.Math.m.sup.2.

(13) A leaching agent as used herein is a chemical or biological agent used in a leaching solution to facilitate solubilization of copper from copper ore and includes any leaching agent known in the prior art to be used for that purpose in acid solution.

(14) The approach to chemically resetting ores disclosed herein involves modifying the operational parameters (e.g., pH, oxidation-reduction potential (ORP), temperature) and solutions applied to the heap. The resetting process achieves its technical effect by chemically removing the passivated layer present on the surface of the mineral particles, exposing the previously hindered surface to be further leached. Through these means, a greater copper recovery from the resulting depassivated mineral in the subsequent leaching stage is achieved.

(15) The phenomenon of surface passivation is observed in copper sulfides derived during leaching or bioleaching processes at the industrial scale. The formation of this passivating coating is attributed to the deposition of chemical products, including elemental sulfur, polysulfides, jarosites, and iron hydroxy compounds, which are the byproducts of the sulfide ore dissolution. The coating obstructs the free diffusion of reagents across the ore surface, thus reducing the kinetics of copper extraction. In bioleaching processes, the growth of microbial communities attached to the surfaces of the mineral particles, simultaneously with a precipitation of ferric ion as jarosites or hydrated ferric oxides in the EPS membranes, generate a passivating layer on the surface of the ore, hindering further copper extraction.

(16) During heap leaching, the physiochemical conditions within the heap along the process change based on the solutions employed and on the chemical reactions occurring during the copper sulfide dissolution. In the context of Cpy-rich ore dissolution, pH and ORP fluctuate, resulting in over saturation and precipitation of certain compounds on the surface of the ore.

(17) Embodiments of the invention comprise a preliminary stage of leaching, during which the pH and ORP are subjected to operational control involving observation and control of the molar ratio of the pair of iron ions [Fe.sup.3+: Fe.sup.2+], and the copper and iron ions [Cu.sup.2+: Fe.sup.3+] present in the leaching solution together with the subsequent monitoring of copper extraction kinetic curve. Such periodic monitoring may facilitate the identification of an inflection point at which the subsequent reset stage may be initiated. In embodiments, the inflection point is the minimum copper extraction rate within a range of 0.1 to 0.2% of copper per day per ton of total copper available in the ore.

(18) Alternatively in non-limiting embodiments, the initial leaching process may be performed in three distinct zones of the ratio ORP/pH: (1) In a reductive zone with a majority of ferrous (Fe.sup.2+) and cupric ions (Cu.sup.2+), with a pH range between 0 and 2 and an ORP range of 200 to 350 mV vs. SHE, as measured at the irrigation solution and the output solution or PLS; (2) in a non-oxidative zone of pH/ORP, the pH levels in a range from 0 to 2, while the ORP levels fluctuate between 400 and 670 mV vs. SHE, and (3) an oxidative zone delineated by a pH range of 0 to 2 and an ORP range of 750 to 800 mV vs. SHE. In further embodiments, this leaching process includes, without limitation, chloride, halide, nitrate or bioleaching.

(19) The reset step, as described in embodiments of the invention, involves the treatment of the ore with a specific reset solution. In one aspect of the invention, the reset solution comprises a chelating agent and a reducing agent. In other embodiments, the reset solution is effective in removing the passive layer that has formed on the surfaces and in the micropores or microchannels of the ore particles, which are primarily composed of jarosite, elemental sulfur and Fe(III)-EPS deposits. In yet another aspect of the invention, the reset solution also contains a sulfur-oxidizing microorganism. In certain embodiments, the reducing agent in the reset solution is an iron-reducer microorganism. In certain embodiments, the treatment of the ore with the reset solution during the reset step produces a Reset pregnant solution (RPS) 24 obtained from the heap.

(20) A reducing agent as used herein is a chemical or biological agent capable of reducing ferric ions (Fe.sup.3+) to ferrous ions (Fe.sup.2+) in the reset solution and acting on the ferric ions as an electron receptor. Specifically, this chemical reduction is facilitated for example by the bisulfite ion (HSO.sub.3.sup.). Ferric ions are present in the ferric precipitates, including hydroxides and jarosites, which form the passivation layer on the ore. The process of elemental sulfur (S.sup.0) conversion to thiosulfate, which ultimately results in sulfate formation, is also a consequence of the effect of the reducing agent in the reset solution in this resetting step. In some embodiments, the reduction of ferric ions present in the precipitates as jarosite, ferrihydrite or ferric hydrate oxide is facilitated by reducing agents such as bisulfite ions, metal bisulfite or dithionite anions, resulting in the liberation of ferrous ions. These reductive reactions are activated synergistically by the immediate and rapid coordination or complexation of Fe(III) and Fe(II) by chelating agents and/or siderophores present in the reset solution. This transport of the precipitated iron passivating the mineral occurs efficiently. These reductions of ferric precipitates occur according to the following chemical reactions:

(21) Ferric reductions by bisulfite HSO.sub.3.sup. in acid solutions:

(22) ##STR00001##

(23) In other embodiments of the invention, elemental sulfur (S.sup.0) is reduced by bisulfite ions. The process contemplates the depassivation of the sulfur deposited on the copper sulfide mineral by different reductive reactions under a complex chain mechanism, until its complete conversion to H.sub.2SO.sub.4, following the set of general equations:

(24) ##STR00002##

(25) The chemical reactions entail the conversion of the passivation elemental sulfur (S.sub.0) on the surface of the chalcopyrite to hydrogen sulfide or hydrogen polysulfide. Subsequently, a conversion of H.sub.2S and H.sub.2S.sub.n (generated in this reductive environment) to thiosalts (with the general formula of S.sub.xO.sub.y.sup.2) occurs, including thiosulfates, dithionates and trithionates. The resulting chemical compounds can be subsequently oxidized to sulfates, thereby eliminating the elemental sulfur (in its forms of S.sup.0 or S8) coating on the chalcopyrite particle.

(26) As used herein, a chelating agent is a chemical or biological agent that facilitates mobilization of metals, including, without limitation, ferric, ferrous, cupric, and cuprous ions at the interface between the ore and the leaching and/or reset solution. This facilitates the removal of these impurities from the heap in further irrigation steps. In conjunction with the reducing agent, a solution is formed that is capable of solubilizing and mobilizing a variable precipitate, including calcium, magnesium, silica, and other species contained in the ore.

(27) In embodiments, the chelating agent may be or may include one or more siderophores, which are small and high-affinity iron-chelating compounds produced by microorganisms. Siderophores bind to ferric iron (Fe.sup.3+) with specificity, forming and transporting soluble iron-siderophore complexes. When in complex with the siderophore, the iron ions may be removed and solubilized from the surface of the ore. The chemical structure of the siderophores may include multiple functional groups capable of coordinating iron. These structures, without limitation, contain ligands like hydroxamates, catecholates and carboxylates which form stable complexes with iron through multidentate interactions forming an octahedral complex such as disclosed in Hider & Kong, Natural product reports 27.5 (2010): 637-657. In embodiments, a chelating agent in the reset solution is selected from the group consisting of citric acid, lactic acid, tartaric acid, ascorbic acid, salicylic acid, tetrasodium glutamate diacetate acid, ethylenediaminetetraacetic acid, pyruvic acid, succinic acid, aspartic acid, gallic acid, fumaric acid, malic acid, gluconic acid, their conjugate bases, or a mixture thereof. In further embodiments, the siderophore in the rest solution is selected from the group consisting of hydroxamates, catecholates, carboxylates or a mixture thereof. In further embodiments, the siderophore in the reset solution comprises nicotinamide, amino acids, enterobactin, ferrichrome, ferrioxamine B, E, G, ferrioxamine D1 to D12, or a mixture thereof. In further embodiments, the siderophore in the reset solution comprises bio-derived molecules from an improved, optimized and/or genetically modified microorganism.

(28) In some embodiments, chelating agents such as Ethylenediaminetetraacetic acid (EDTA) form coordinating chemical structures with the iron ions, rendering them soluble in aqueous solutions (aq) according to the following general equation:

(29) ##STR00003##

(30) In another embodiment of the invention, the chemical complex formed between iron and citrate in an acidic aqueous solution works as the following general equations:

(31) ##STR00004##

(32) In addition to citrate and EDTA, other chelating agents may be used. In embodiments, the complexation of Fe.sup.3+ and the chelating agent tetrasodium glutamate diacetate acid (GLDA) is in accordance with the following general equations:

(33) ##STR00005##

(34) As depicted in FIG. 1, in accordance with an exemplary embodiment of the present invention, the method may comprise three steps (A), (B) and (C) conducted in order. Additionally, processing may occur between these three steps. The initial step (A) involves providing a heap of previously leached copper ore 10. In the second step (B), the heap is treated with a reset solution 20 in reducing conditions. The third step (C) involves subjecting the ore to a leaching process. Thus, the reset step is separated from prior or subsequent leaching processes. As depicted in FIG. 1, reset solution may be processed in and provided from process unit 1, 22 including one or more mixing tanks receiving make-up reagents and reset reagents to formulate and reconstitute the reset solution, and leaching solution may be processed in and provided from process unit 2, 32 including one or more mixing tanks receiving make-up reagents and leaching reagents to formulate and reconstitute the reset solution. This allows for control of copper ore resetting through the adjustment of process variables, including pH and redox potential. Furthermore, this process enables more effective treatment of insoluble species, such as ferric-derived ions or elemental sulfur (S.sub.0). Finally, the resetting step prevents unintended chemical reactions between the reset solution and the leaching solution, which may result in the production of undesirable by-products and potentially affect the effectiveness of the reset treatment.

(35) The ore may be subjected to a process of crushing, agglomeration and curing, as described in detail below or as described in the prior art. For example, in some embodiments, the ore may be crushed to a P.sub.100 particle size prior to forming the heap. This may entail a particle size distribution in which 100 percent of particles are less than 1 inch, with a range between about inch to about 1 inch. It is preferable that the ore be crushed prior to the agglomeration step, which is performed before the leaching step and/or the reset step. Crushing involves a mechanical reduction of the ore size. In some embodiments, this reduction is to a range wherein 100% of the particles are smaller than inch (at one end of the range) and up to 100% of the particles are smaller than inch (at the upper end of the range). In conventional stockpile operations, agglomeration is conducted as a subsequent step following crushing and prior to stockpiling. This involves the application of a concentrated mixture of sulfuric acid, water, and/or raffinate (derived from the solvent extraction (SX) stage) to the mineral.

(36) In some embodiments, the agglomeration step may be conducted subsequent to the additional crushing step. This step involves the mechanical fractioning of the ore, with the objective of increasing its surface area. In some embodiments, the agglomeration step comprises wetting and adding concentrated sulfuric acid, which facilitates the adhesion of the fine particle fraction to larger particles. This process generates hydraulically and mechanically stable ore agglomerates. The ore wetting may be performed while the ore is being agglomerated, in an agglomeration drum or using other wetting systems. In some embodiments, gases produced in the agglomerating and curing steps may be treated in a gas scrubber to remove undesirable chemical species. Subsequently, an additional step of agglomerated ore stacking may comprise the transportation of the agglomerated ore from the additional agglomeration step to the leach heap via conveyor belts.

(37) As an alternative, the ore may be wetted during ore stacking. The wetting of the ore, in the additional stacking step, may be carried out on conveyor belts that transport the ore to the leach heap, or by another equivalent method, depending on the loading procedures employed.

(38) As an alternative, the ore may be stacked and leached (without being crushed and agglomerated previously) in large leach pads, as described in the art.

(39) In accordance with an embodiment of the invention, the heap of copper ore is subjected to any of the processes described in the art for leaching copper from copper containing material comprising copper sulfides to provide ore previously leached. Prior to the reset step, the heap may undergo a leaching step (C) using sulfuric acid, solutions comprising ferric ions, chloride ions, or nitrate ions; copper-depleted raffinate; microorganisms; or a combination of these. In embodiments, the leaching step produces a pregnant leaching solution (PLS) 34.

(40) In further embodiments, a reset pregnant solution (RPS) is recovered from the heap during the reset step. In some embodiments, the RPS is treated to obtain a copper depleted reset solution which is circulated to the reset solution and a copper-enriched containing solution. In further embodiments, the concentration of copper in the RPS recovered during the reset step and in the depleted reset solution and the copper-enriched containing solution obtained through the treatment of said reset pregnant solution is in the range of 8 mM to 65 mM, below 8 mM, and above 30 mM respectively. In further embodiments, the treatment of the RPS comprises physical separation techniques, solid-liquid extraction, liquid-liquid extraction, reverse/forward osmosis, electrocoagulation, electrodialysis, chemical precipitation or a combination thereof. Physical separation techniques aim at separate the components of heterogeneous or homogeneous mixtures without altering their chemical composition and include any method such as settling, decantation, filtration, evaporation, crystallization and centrifugation, or mixtures thereof as described in the art. Solid-liquid extraction separates metals of interest from an aqueous solution by means of a selective solid phase, such as ion exchange, or through any other method described in the art. Liquid-liquid extraction aims at separating metals of interests by using two immiscible or partially immiscible liquids having different solubilities of the metal of interest. Liquid-liquid extraction may be performed through solvent extraction, ionic liquids or through any other such techniques described in the art. Reverse/forward osmosis is able to either concentrate or to separate the metals of interest from an aqueous solution through the use of semi-permeable membranes. Electrocoagulation aims at either concentrating or separating the metals of interest from an aqueous solution by applying an electric current through two electrodes to an electrolytic solution. Chemical precipitation aims to precipitate the metal of interest by applying a chemical agent such as aluminum and iron salts, or others as described in the art. Electrodialysis concentrates and/or separates metals of interest by using electrical electrodes to move ions through semi-permeable membranes. In some embodiments, the RPS is further treated in treatment tank 26, to obtain a copper depleted reset solution and a copper-enriched containing solution. In further embodiments, the copper-enriched containing solution obtained through the treatment of the RPS may be then advanced to PLS pond 36 and processed according to techniques known in the art. Subsequently, the PLS from the PLS pond may be pumped to a solvent extraction (SX) process for the separation and recovery of copper. Subsequently, two streams are produced: a copper-rich electrolyte solution that is advanced to the EW process and a raffinate solution, which is the aqueous phase from the SX. This copper-depleted raffinate may form part of the leaching solution used for heap irrigation. In some embodiments, the average volume of leaching solution irrigated is between 2 and 43 liter per kilogram of ore. However, any volume of leaching solution and leaching protocol known in the art may also be used.

(41) In reference to FIG. 1, the ore at (A) may undergo agglomeration, subsequent transportation to the stockpile formation, and leaching using conventional solutions before the reset solution irrigation (B). Both leaching steps (A) and (C) are conducted until the point at which copper extraction is no longer feasible.

(42) With reference to FIG. 1, the copper ore reset step (B) may involve the irrigation of copper ore with a reset solution comprising a chelating agent and a reducing agent. The molar ratio of the chelating agent to the reducing agent in the reset solution may be within the range of 4:1 to 1:100. The concentration of the reducing agent in the reset solution may be between 10 and 1000 mM. In some embodiments, the chelating agent in the reset solution is selected from the group consisting of citric acid, lactic acid, tartaric acid, ascorbic acid, salicylic acid, tetrasodium glutamate diacetate acid, ethylenediaminetetraacetic acid, pyruvic acid, succinic acid, aspartic acid, gallic acid, fumaric acid, malic acid, gluconic acid, their conjugate bases, or a mixture thereof. The amount of chelating agent used is preferably sufficient to improve iron solubilization. The reset solution used in the reset step has a pH in a range of 2 to 6 and a redox potential ranging from 200 to 700 mV. The reset solution may be formulated in a pond or series of ponds, which receive the reducing agent and the chelating agent as inputs. These inputs may be provided in the form of aqueous solutions, which are held in tanks and pumped through conventional piping. As illustrated in FIG. 1, the term Process Unit 1 denotes a pond or series of ponds where the reset solution may be formulated. In some embodiments, the reset step produces a reset pregnant solution which is recovered and treated to obtain a copper depleted reset solution which is recirculated to the reset solution, and a copper-enriched containing solution. The reset pregnant solution is derived from a heap that has undergone a reset process and contains copper ore by-products, including copper and iron ions. In some embodiments, the reset pregnant solution has a copper concentration in the range of 8 to 65 mM. In some embodiments, the reset pregnant solution is treated through physical separation techniques, solid-liquid extraction, liquid-liquid extraction, reverse/forward osmosis, electrocoagulation, electrodialysis, chemical precipitation or a combination thereof to obtain a copper depleted reset solution and a copper-enriched containing solution. In further embodiments, the concentration of copper in the copper depleted reset solution and in the copper-enriched containing solution is in the range of below 8 mM and above 30 mM respectively. In some embodiments, the reducing agent in the reset solution is effective for iron solubilization and sulfur conversion. This may include the reduction of Fe.sup.3+ to Fe.sup.2+ and the conversion of elemental sulfur to thiosulfate or another chemical species, which generates sulfate in the final stage. The reducing agent in the reset solution may comprise bisulfite ion, dithionite ion, metabisulfite ion, or a mixture of these. In some embodiments, prior to performing the reset step, the heap is irrigated with a conditioning solution having a pH in a range of 3.5 to 14 in a conditioning step. In further embodiments, the conditioning solution in the conditioning step comprises a buffering agent. In other embodiments, the conditioning solution in the conditioning step further comprises raffinate. In further embodiments, the buffering agent of the conditioning solution is selected from the group consisting of citric acid, lactic acid, tartaric acid, ascorbic acid, salicylic acid, tetrasodium glutamate diacetate acid, ethylenediaminetetraacetic acid, pyruvic acid, succinic acid, aspartic acid, gallic acid, fumaric acid, malic acid, their conjugate bases, and a mixture thereof. In other embodiments, the concentration of the buffering agent in the conditioning solution is above 50 mM. In further embodiments, the conditioning solution comprises a reducing agent in a concentration less than 0.1 mM. The conditioning step is conducted up to the point in which the heap reaches at least a pH of 3.5. This allows for buffering the reset solution at the heap in a range of pH between 3.5 to 14. The buffering effect minimizes the risk of the generation of sulfur oxides (SO.sub.x) gases during the readjustment step and to remove salts or other residues from the previous leaching step.

(43) In other embodiments, the sulfur-oxidizing microorganism for elemental sulfur solubilization may be selected from the genera Acidithiobacillus, Acidiphilium, Acidicaldus, Acidiferrobacter, Acidihalobacter, Alicyclobacillus, Sulfobacillus, Hydrogenobaculum, Acidithiomicrobium, and mixtures thereof.

(44) In embodiments of the invention, the reset step is executed within a time frame of between 10 and 40 days. In embodiments, the reset solution is irrigated at a ratio of between 0.1 and 8 liters of reset solution per kilogram of ore.

(45) Following the reset step, a subsequent stage of leaching may be initiated, whereby the heap may be irrigated with a variety of solutions, including sulfuric acid, solutions comprising ferric ions, chloride ions, or nitrate ions, copper-depleted raffinate, microorganisms, and mixtures thereof. The reset process of the present invention may be adapted to different leaching processes and will enhance copper recovery regardless of the leaching technology employed. The Process Unit 2 denotes a pond or a series of ponds in which a leaching solution may be formulated and receives inputs such as the microorganisms from the microbial biomass process unit 35 (if necessary), and/or copper-depleted raffinate and other reagents from a leaching reagents process unit. In further embodiments, the reset solution and the leaching steps can be repeated cyclically over the passivated copper ore. Piping may be provided to remove ILS or PLS from the leached second heap.

(46) In some embodiments, the leaching irrigation step over the copper-ore containing material produces a pregnant leaching solution (PLS) that may be advanced to the PLS pond and subsequently processed according to techniques that are well known in the art. Subsequently, the PLS from the PLS pond is pumped to a solvent extraction (SX) process 37 for the separation and recovery of copper. Subsequently, two streams are produced: a copper-rich electrolyte solution that is advanced to the electrowinning (EW) process 42 and a raffinate solution, which is the aqueous phase from the solvent extraction (SX) process. This copper-depleted raffinate may form part of the leaching solution. In some embodiments, the average volume of leaching solution irrigated is between 2 and 4 liters per kilogram of ore. However, any volume of leaching solution and leaching protocol known in the art may also be used.

(47) In another aspect of the invention, the microorganism component of the reset solution and the microorganism component of the leaching solution are produced through biomass augmentation for use in the reset step or in the leaching step over the copper ore. With reference to FIG. 1, the microorganism component of the leaching solutions is produced in the microbial biomass process unit 35.

(48) The microbial biomass process unit denotes a biomass platform comprising at least one bioreactor with an inlet for nutrient and/or chemical substance sources, an inlet for microbial inoculum, and an output of reset-related biomass (to provide sulfur-oxidizing or iron reducer microorganisms to the reset solution) or leaching-related biomass (to provide bioleaching microorganisms to the leaching solution).

(49) In other embodiments, the invention is a method to generate acid comprising a) providing ore comprising sulfur; (b) treating said ore with a releasing solution comprising a releasing agent and; c) collecting the acid of the bottom of the ore. In further embodiments, the releasing agent in the releasing solution is selected from the group consisting of chelating agents and/or reducing agents. In further embodiments, the chelating agents in the releasing solution are citric acid, lactic acid, tartaric acid, ascorbic acid, salicylic acid, tetrasodium glutamate diacetate acid, ethylenediaminetetraacetic acid, pyruvic acid, succinic acid, aspartic acid, gallic acid, fumaric acid, malic acid, or a mixture thereof. In further embodiments, the reducing agents in the releasing solution are bisulfite ion, dithionite ion, metabisulfite ion, and a mixture thereof. In further embodiments, the acid thusly collected is recirculated into a heap to be used to further leaching. In other embodiments, the acid thusly collected is treated in a treatment tank previous to its recirculation into a heap. In further embodiments, the acid thusly collected is redirected and used in a different industrial process.

(50) In other embodiments, the invention is a method for generating acidified conditions on a heap of ore comprising a) providing ore comprising sulfur and (b) treating said ore with a releasing solution comprising a releasing agent. In further embodiments, the releasing agent in the releasing solution is selected from the group consisting of chelating agents and/or reducing agents. In further embodiments, the chelating agents in the releasing solution are citric acid, lactic acid, tartaric acid, ascorbic acid, salicylic acid, tetrasodium glutamate diacetate acid, ethylenediaminetetraacetic acid, pyruvic acid, succinic acid, aspartic acid, gallic acid, fumaric acid, malic acid, or a mixture thereof. In further embodiments, the reducing agents in the releasing solution are bisulfite ion, dithionite ion, metabisulfite ion, and a mixture thereof.

EXAMPLES

Example 1

(51) In a working example, for the preparation of the reset solution, 969 g of water was poured into a 2 L beaker. Then, with stirring, 4.9 mL of 40% citric acid was added. After its dissolution, 62.4 g of sodium bisulfite was slowly added to the agitated mixture. Stirring was stopped when the bisulfite salt was completely dissolved. The resulting 1 L reset solution contained 600 mM of sodium bisulfite, 10 mM of citric acid, and a pH of 3.2.

Example 2Iron Removal

(52) FIGS. 2, 3 and 4 depict the solubilization of iron from passivated copper ore. Copper ore, composed mainly of primary copper sulfide ore (about 84-95% of the contained copper as chalcopyrite), and to a lesser extent, secondary copper sulfide ore (up to 10% of the contained copper as covellite, and up to 10% of the contained ore as a chalcocite/digenite), with an ore size of P.sub.800.18 inch, was passivated to facilitate the precipitation of ferrous hydroxides (e.g. jarosite). To passivate the ore, the material was first subjected to a chemical treatment with synthetic raffinate, composed mainly of aluminum, potassium, sodium and iron ions dissolved in diluted sulfuric acid, with a pH less than 1.2, and for 10 days. Subsequently, the treated material was subjected to chemical characterization with XRD to confirm the presence of iron precipitates (about 10% of jarosite).

(53) The effect of the reset solution may be observed as the solubilization of undesirable species, such as iron hydroxy compounds, from the surface of the passivated ore. This allows copper occluded in the ore to be leached subsequently. Following the ore treatment, an increase in iron concentration in the reset solution is expected, which is indicative of the solubilization of iron. The iron extraction is shown based on the total iron in the sample, including the percentage of iron in the ore and the iron precipitates generated during ore passivation.

(54) For FIG. 2, six laboratory flasks were prepared, each containing the same quantity of passivated copper ore. Subsequently, each flask containing the corresponding material was treated with the same volume of each different reset solution described in Table I below. This was done to assess the effect of variants of reducing and chelating agents. Each flask was continuously stirred for 10 days at 30 C. Finally, a sample of the liquid supernatant, along with the residual solids from each flask was collected and the iron content of each sample was determined. For comparison purposes, a flask containing passivated ore treated with water at pH 4.5 was also included (as the water flask in FIG. 2). The iron extraction of each reset solution was calculated as a percentage of the amount of iron extracted from the passivated ore at the end of resetting period of the flask, relative to the total amount of iron presented in the initial ore sample.

(55) TABLE-US-00001 TABLE I Variants of reducing and chelating agents employed in each reset solution Flask ID Reducing agent Chelating agent R:C Ratio pH F1 Sodium dithionite (0.6M) Ascorbic acid (0.01M) 60:1 4.5 F2 Sodium metabisulfite (0.6M) Ascorbic acid (0.01M) 60:1 4.5 F3 Sodium metabisulfite (0.6M) EDTA (0.01M) 60:1 4.5 F4 Sodium metabisulfite (0.6M) GLDA (0.01M) 60:1 4.5 F5 Sodium bisulfite (0.6M) Ascorbic acid (0.01M) 60:1 4.5 F6 Sodium bisulfite (0.6M) Citric acid (0.01M) 60:1 4.5

(56) In a further experiment, and related to FIG. 3, three laboratory flasks were prepared, each containing the same quantity of passivated copper ore. Subsequently, each flask containing the corresponding material was treated with the same volume of each different reset solution described in Table II below. This was done to assess the effect of the reducing-chelating ratio (R: C). Each flask was continuously stirred for 10 days and at 30 C. Finally, a sample of the liquid supernatant, along with the residual solids from each flask were collected and the iron content of each sample was determined. For comparison purposes, a flask containing passivated ore treated with water at pH 4.5 was also included (as the water flask in FIG. 3). The relative iron removal of each reset solution was calculated as a percentage of iron extraction, in comparison to the reset solution with the highest iron removal disclosed herein (R: C ratio of 60:1).

(57) TABLE-US-00002 TABLE II Reducing-Chelating (R:C) ratios employed in each reset solution Flask ID Reducing agent Chelating agent R:C Ratio pH F1 Sodium dithionite (1M) Citric acid (0.01M) 100:1 4.5 F2 Sodium dithionite (0.6M) Citric acid (0.01M) 60:1 4.5 F3 Sodium dithionite (0.1M) Citric acid (0.4M) 1:4 4.5

(58) In a further experiment, and related to FIG. 4, three laboratory flasks were prepared, each containing the same quantity of passivated copper ore. Subsequently, each flask containing the corresponding material was treated with the same volume of each different solutions described in Table III below. This was done to assess the combined effect of both reducing and chelating compounds. Each flask was continuously stirred for 10 days at 30 C. Finally, a sample of the liquid supernatant, along with the residual solids from each flask was collected and the iron content of each sample was determined. The iron removal of the reducing and the chelating agent was calculated as a relative iron removal (%), in comparison to the iron removal of the reset solution with both the reducing and chelating agent.

(59) TABLE-US-00003 TABLE III Synergistic effect of the compound in the reset solution Flask ID Reducing agent Chelating agent pH C Citric acid (0.01M) 4.5 R Sodium Dithionite (0.6M) 4.5 R + C Sodium Dithionite (0.6M) Citric acid (0.01M) 4.5

(60) In the example of FIG. 2, and related to Table I, the iron extraction rate was between 7% and 14%, which was significantly higher than the iron extraction obtained solely with water (approximately 0.5%). The flasks tested the reset solutions with different variants of reducing agents (such as dithionite, bisulfite and metabisulfite) and different variants of chelating agents (such as ascorbic acid, citric acid, EDTA and GLDA) demonstrated comparable iron extraction, confirming the effectiveness of each chemical equivalent that composes the reset solution. It is expected that higher iron removal can be achieved with an extended resetting time and in a continuous irrigation system, which is a feature of any heap ore irrigation process. It is also important to note that the composition of the reset solution used in the Flask N6 is similar to that used in the leaching column experiment of the Example 3 (0.6 M sodium bisulfite with 10 mM citric acid, pH 4.5).

(61) In the example of FIG. 3, and related to Table II, the efficacy of each reset solution in terms of iron removal is contingent upon the concentration of each the reducing and the chelating agents, as well as the R: C ratio. It is evident in this experiment that the highest iron removal was achieved with a reset solution comprising 0.6 M of reducing agent and 0.01 M of chelating agent (F2). Higher concentrations of reducing agents did not result in improved iron removal (F1). Similarly, low amounts of reducing agents and high amounts of chelating agents also did not result in improved iron removal (F3). These results suggest that intermediate values of R: C ratio, as well as chelating and reducing agent concentration values are necessary for an optimal iron removal and preparation of the depassivated ore for the subsequent leaching step.

(62) In the example of FIG. 4, and related to Table III, using only the chelating (C) or the reducing (R) agent in the reset solution, losses about 30% of the relative iron removal which is obtained when the chelating and reducing agents are used together. This demonstrates a synergistic effect when the compounds in the reset solution are used in combination. Although the chelating agent is typically described as a molecule that can coordinate iron ions, it is expected that, in conjunction with the reducing agent, the chelating agent will gain a new feature that will enhance the iron release from the passivated mineral.

Example 3Leaching Columns

(63) FIG. 5 depicts copper recovery with a leaching column system adapted for leaching copper sulfide ores, and FIG. 6 illustrates the pH and ORP measurements taken during the experimental phase. The copper ore, composed mainly of primary copper sulfide ore (about 84-95% of the contained copper as chalcopyrite), and to a lesser extent, secondary copper sulfide ore (up to 10% of the contained copper as covellite, and up to 10% of the contained ore as a chalcocite/digenite), with an ore size of P.sub.80 0.18 inch, was first subjected to an agglomeration step with sulfuric acid and water. Then, the leaching column was filled with approximately 1 kg of the agglomerated ore. The loaded ore was subjected to a leaching step by irrigating the column with a leaching solution comprising microorganisms for 67 days (0.4% sulfuric acid; pH<2, irrigation rate 5 L/h/m.sup.2; using 510.sup.6 cel/mL of a consortium consisting primarily of Acidithiobacillus ferrooxidans and Leptospirillum spp). Following the copper recovery parameter in each of FIG. 5 and operating conditions in FIG. 6 over the course of time, it was found that no more copper in the mineral could be extracted after about day 60. The column was then treated with the reset solution (0.6 M sodium bisulfite; 10 mM citric acid; pH 3.5; irrigation rate 5 L/h/m.sup.2), for the next 20 days. The reset solution treated the leached ore, allowing the hindered copper in the mineral to be available again. Finally, the column was again subjected to a leaching step with the same leaching solution containing microorganisms (0.4% sulfuric acid, pH<2; irrigation rate 5 L/h/m.sup.2; 510.sup.6 cel/mL of a consortium consisting primarily of Acidithiobacillus ferrooxidans and Leptospirillum spp). FIG. 5 shows the copper recovery achieved after applying the reset solution in the process, while FIG. 6 shows the operating parameters for the reset step. Further leaching-reset-leaching steps could be applied in the leaching column, as well as applied in a copper heap, in order to extract more copper from the respective sulfide ores.

(64) Table IV depicts a summary of copper recovery with a leaching column system adapted for leaching copper sulfide ores. Two different leaching setups were used: acid leaching and nitrate leaching.

(65) For the acid leaching, the copper ore, composed mainly of primary copper sulfide ore (about 84-95% of the contained copper as chalcopyrite), and to a lesser extent, secondary copper sulfide ore (up to 10% of the contained copper as covellite, and up to 10% of the contained ore as a chalcocite/digenite), and with an ore size of P.sub.800.18 inch, was first subjected to an agglomeration step with sulfuric acid and water. Then, the leaching column was filled with approximately 1 kg of agglomerated ore. The loaded ore was subjected to a leaching step by irrigating the column with a leaching solution comprising ferric ions for 39 days (10 g/L sulfuric acid; 5 g/L ferric ions; pH <2; irrigation rate 5 L/h/m.sup.2). The column was then treated with a conditioning solution, comprising citric acid with citrate at pH 5, for 2 days. After this, the column was treated with the reset solution (0.6 M dithionite; 10 mM citric acid; pH 4.5; irrigation rate 5 L/h/m.sup.2) for the next 20 days. The reset solution treated the leached ore, allowing the hindered copper in the mineral to be available again. Finally, the column was subjected to a leaching step with the same leaching solution of the first stage, for 7 days. To compare the effect of the reset step, a column with the same experimental design, but without the use of the reset step, was included. This column was subjected solely to the specified acid leaching conditions throughout the duration of the test.

(66) For the nitrate leaching, the copper ore, composed mainly of primary copper sulfide ore (about 84-95% of the contained copper as chalcopyrite), and to a lesser extent, secondary copper sulfide ore (up to 10% of the contained copper as covellite, and up to 10% of the contained ore as a chalcocite/digenite), and with an ore size of P.sub.80 inch, was first subjected to an agglomeration step with sulfuric acid, nitrate and water. Then, the leaching column was filled with approximately 1 kg of agglomerated ore. The loaded ore was subjected to a leaching step by irrigating the column with a leaching solution comprising nitrate anions for 39 days (10 g/L sulfuric acid, 7.5 g/L nitrate anions, pH<2; irrigation rate 5 L/h/m.sup.2). It must be noted that around day 25, the operational parameters (pH and ORP) were altered in order to promote iron hydroxides precipitation, i.e. ore passivation. The column was then treated with a conditioning solution, comprising citric acid with citrate at pH 5, for 2 days. After this, the column was then treated with the reset solution (0.6 M dithionite, 10 mM citric acid, pH 4.5, irrigation rate 5 L/h/m.sup.2) for the next 20 days. The reset solution treated the leached ore, allowing the hindered copper in the mineral to be available again. Finally, the column was subjected to a leaching step with the same leaching solution of the first stage, for 7 days. To compare the effect of the reset step, a column with the same experimental design, but without the use of the reset step, was included. This column was subjected solely to the specified nitrate leaching conditions throughout the duration of the test.

(67) FIG. 4 shows the copper recovery achieved after applying the reset solution in the process, while FIG. 5 shows the operating parameters for the reset step. Further leaching-reset-leaching steps could be applied in the leaching column, as well as applied in a copper heap, in order to extract more copper from the respective sulfide ores.

(68) TABLE-US-00004 TABLE IV Leaching results using the reset step onto different leaching methods Copper recovery Enhanced copper Column [%] at day 68 extraction Acid leaching 24% 1.37 Acid leaching with reset step 33% Nitrate leaching 26% 1.22 Nitrate leaching with reset step 33%

(69) The term Enhanced copper extraction may be defined as an increase in copper recovery compared to the maximum recovery achieved with a given leaching solution for a given ore in a single leaching step (baseline). In the example of FIG. 5 a maximum copper recovery of 14% is attained at about 60 days. It is expected that these leaching days may vary when different leaching technologies are used. However, that maximum recovery will always be characterized by a levelling off the metal recovery curve after several days. After reset, further copper recovery is possible. The results depicted in FIG. 5 demonstrate a significant increase in copper extraction at the end of the second leaching step (day 140) with a copper extraction of 22.5%, meaning an enhanced copper extraction of 1.6times compared to the baseline Using the techniques of the invention, an enhanced copper extraction of about 1.6 and about an average of 1.3 were observed in FIG. 5 and Table IV, respectively. This invention increases the overall copper extraction by 1.2 to 2 compared to the baseline. The operational conditions illustrated in FIG. 6, corresponding to the experiments depicted in FIG. 5, demonstrate the obligatory alterations of the ORP and pH that are required to facilitate the unlocking of the passivated copper ore with the reset solution, thus preparing the ore for the subsequent leaching step.

Example 4Electronic Microscopy

(70) FIG. 7A, 7B, 7C, 7D, 7E and 7F depict the impact of the reset solution on the surface of the copper ore obtained from the column treated in accordance with the example illustrated in Table IV and FIG. 4. The surface of the samples was analyzed using scanning electron microscopy with energy-dispersive X-ray spectroscopy spectrum (SEM-EDS). In particular, the ore samples analyzed in FIG. 7A through FIG. 7F were obtained with the head ore without any leaching step, after the first leaching step, and after the application of the reset solution, respectively. SEM-EDS analysis of FIG. 7A and FIG. 7B shows the ore prior to the leaching step. On the surface of the ore there were no iron precipitates and there were zones with visual copper particles attributable to chalcopyrite available on the surface. The SEM-EDS analysis in FIG. 7C and FIG. 7D revealed that the ore surface was primarily covered with sulfur and precipitated iron, likely corresponding to jarosite. The presence of copper on the ore surface was low likely due to the precipitation of iron hydroxide and sulfur derived salts. By contrast, the analyses in FIG. 7E and FIG. 7F revealed that the treated ore surface had an increase in copper availability. These results demonstrate the effectiveness of the reset solution, and its corresponding reset stage, as an evident removal of the accumulation of iron and sulfur from the ore surface, thereby restoring the availability of copper for further leaching.

Example 5Sulfur Removal

(71) The effect of the reset solution may also be observed as the solubilization of undesirable species, such as elemental sulfur compounds, from the surface of the passivated ore. This allows copper occluded in the ore to be leached subsequently. Following the ore treatment, an increase in the presence of sulfur in the reset pregnant solution is expected, which is indicative of its solubilization.

(72) In a leaching column system, copper ore was leached following the conditions set forth Example 3Table IV. After a leaching period of 39 days, columns were washed and subsequently discharged. A representative sample of the discharged material was taken and analyzed using X-ray photoelectron spectroscopy (XPS) to demonstrate the presence of sulfur-derived salts. In FIG. 8A and FIG. 8B, the intensity (counts per second) of the electrons was plotted against their binding energies (eV). This technique enables the identification of the chemical compound to which the surface-bound sulfur belongs. The results showed the presence of binding energy for signals attributable to sulfites, sulfates and/or thiosulfites in the passivated ore sample (FIG. 8A), but not in the treated sample (FIG. 8B), demonstrating the effectiveness of the reset solution in removing sulfur salts from the surface of passivated ores.

(73) Finally, the aforesaid results demonstrate that the Reset solution, and the corresponding reset step, are capable of treating copper ore that has been previously leached and therefore passivated. This process effectively removes undesirable species, such as iron hydroxy compounds and sulfur compounds, which are typically formed when the ore is leached. Consequently, the treated ore can be prepared for further copper extraction through leaching without additional re-crushing or remining.

(74) Different embodiments are disclosed herein. Features of certain embodiments may be combined with features of other embodiments; thus, certain embodiments may be combinations of features of multiple embodiments. Likewise, in the following claims a feature expressed in a dependent claim may be combined with a different independent claim and/or with the features of other dependent claims. The foregoing description of the embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. It should be appreciated by people skilled in the art that many modifications, variations, substitutions, changes, and equivalents are possible in light of the above teaching. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.

(75) While certain features of the invention have been illustrated and described herein, many modifications, substitutions, changes and equivalents will now occur to those of ordinary skill in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.

(76) Unless explicitly stated, different process or method steps described herein with regard to different embodiments of the invention may not be constrained to a particular order or sequence. Additionally, some of the described method embodiments or elements thereof can occur or be performed simultaneously, at the same point in time, or concurrently.