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    Abstract A Method for the Recovery of Indium, Silver, Gold and Other Precious and Rare Base Metals from Complex Oxide and Sulphide Ore The present invention relates to methods for the recovery of precious metals, including silver and gold, metals. rare, including indium and gallium, base metals including copper, lead and zinc or a combination of rare and precious base metals from complex oxide ores, sulfide ores and oxide and sulfide ores, using chloride oxidizing bleach of acid. the process comprises contacting the ore with an acid, a chloride salt and a soluble oxidant under a selected condition to form an ore residue and an acid soluble oxidant bleach solution comprising the metals; and separating the acid-soluble oxidant bleach solution from the ore residue.
    公开号:BR112013028340B1
    申请号:R112013028340-8
    申请日:2012-04-20
    公开日:2019-01-15
    发明作者:Ralph FITCH；Niels Verbaan；David Dreisinger
    申请人:Trimetals Mining Inc.；
    IPC主号:
    专利说明:

    METHOD FOR THE RECOVERY OF A METAL FROM A ORE
    Field of the invention [01] The present invention generally relates to a process for recovering metals from ores. More particularly, the present invention relates to the recovery of precious metals, including silver and gold, rare metals, including indium and gallium, or base metals, including copper, lead and zinc, or a combination of base, precious and rare metals from complex oxide and sulfide ores, or from a combination of oxide and sulfide ores using leaching with oxidizing acid.
    Basics of the invention [02] The concentration of indium in the earth's crust is approximately 0.25 ppm by weight. Economic Indian ores are rarely found in nature. Indium is usually recovered as a by-product of zinc or copper concentrate treatment. For example, at the Dowa refinery in Lijima, Japan, the indium is extracted in a solution of sulfuric acid and by adjusting the pH, it is precipitated as a crude indium hydroxide product. Indium hydroxide is then refined to pure indium (usually approximately 99.99% purity) using a series of chemical dissolution and precipitation steps in combination with solvent extraction and electrochemical reduction for metal.
    [03] Likewise, indium-rich smokes from zinc vaporization operations (eg, carbothermic reduction of lead slag) or indium-rich dust from copper smelting operations are often processed using leaching and acid precipitation to produce indium hydroxide products for refining.
    [04] Indium is in high demand for use in many high-tech applications, including indium tin oxide (ITO) in liquid crystal displays and touch screens, high-efficiency thin-film solar panels or lighting LED and fiber optics.
    [05] The supply of Indian is generally restricted due to the direct connection
    2/28 with the production of copper or zinc in the producer's facilities. In order to advance and expand Indian applications, it is desirable to develop new resources. The Malku Khota deposit in Bolivia contains a mixture of valuable metals, including indium, silver, gold, copper, lead, zinc, gallium and other rare metals. Summary [06] In several modalities, a method is provided for the recovery of a metal from an ore, which in several modalities can be an oxide ore, a sulfide ore or a combination of oxide and sulfide ores. In various modalities, the metal can be a rare metal ore, precious metal, base metal or a combination of these. The method comprises:
    (a) contacting the ore with an acid, a chloride salt and a soluble oxidant under a selected condition to form an ore residue and an acid-soluble oxidizer bleach solution comprising the metal; and (b) separating the bleach solution from acid-soluble oxidizer from the ore residues.
    [07] In several modalities, the metal can, for example, be one or more of In, Ag, Au, Pb, Cu, Zn, Ga. In various embodiments, the acid can be, for example, sulfuric acid, hydrochloric acid or a combination of these. In various embodiments, sulfuric acid or hydrochloric acid can be used, for example, in concentrations ranging from approximately 10 g / L to 100 g / L of acid. In several embodiments, the chloride salt can be, for example, sodium chloride, potassium chloride, calcium chloride, magnesium chloride or salt that can be a source of chloride in the solution to stabilize the dissolved metals as metal-complexes. chloride. In various embodiments, the soluble oxidizer comprises, for example, sodium hypochlorite, sodium chlorate, sodium chlorite and other oxidants, such as, for example, chlorine gas, hypochlorous acid (HOCI), Caro H2SO5 acid or a combination thereof . In various embodiments, the chloride salt can be used in concentrations ranging from approximately 1 to 3.5 mol / L. The acid-soluble oxidant bleach solution may include an acyl chloride bleach solution. In various ways, the step of contacting
    3/28 the ore leacher may, for example, involve pile leaching, tank leaching, agitated reactor leaching, mixing or a combination of these. The selected conditions can include a selected temperature, such as from room temperature to a boiling point. In various embodiments, oxide ores, sulfide ores or a combination of these can be pre-treated, for example, by dry grinding, wet grinding or a combination of these processes. In various embodiments, pretreatment can be done to produce particles ranging in size from approximately 1/8 inch to 1 inch or more and / or to produce a fine ore material and a thick ore material. The fine ore material and the thick ore material can be treated separately using the methods of the invention. In selected embodiments, the concentration of the acid can be modulated in the acid-soluble oxidizer bleach solution, for example, by the acid recovery from the acid-soluble oxidant bleach solution to form a recovered acid and a low-lye solution acid comprising a residual acid. In various embodiments, the recovery of the acid can be carried out using a solvent extraction which comprises bringing the acid-soluble oxidizing bleach solution with a solvent into contact with a solvent to form a charged solvent, comprising an extracted species. In several embodiments, the solvent is an extraction solvent, consisting of an alkyl phosphate, an alkyl phosphonate, an alkyl phosphinate or a combination of these. In several embodiments, the alkyl phosphate is tri-butyl phosphate, the alkyl phosphonate is di-butyl butyl phosphonate and the alkyl phosphinate is Cyanex 923. In several embodiments, the species extracted is a species of iron chloride -hydrochloric acid (for example, HFeCU).
    [08] In various embodiments, the charged solvent can be cleaned with an aqueous solution (eg water) to form a washed loaded solvent comprising FeCI 3 and HCl and then removed with additional aqueous solution (eg water) to displace FeCI 3 and HCl (form a
    4/28 solution made up of FeChe HCI). In several embodiments, the solution consisting of FeCh and HCI is pre-evaporated to form a pre-evaporated FeCh and HCI solution and can further be thermally decomposed (for example, spray roasting, pyrohydrolysis, heating or a combination of these) to produce hematite and regenerate hydrochloric acid.
    [09] The recovered acid can, for example, be recycled to the contact stage and the hematite can be recovered as a valuable product. Neutralization of the residual acid acid from the acid-poor bleach solution can also be done, for example, by placing the acid-poor bleach solution in contact with a neutralizing agent, such as calcium carbonate, dolomite, lime, sodium hydroxide or a combination of these. A separation step can be used to recover the metal from the acid-poor bleach solution, such as carburizing, precipitation or a combination of these. In several other embodiments, precipitation may involve a pH adjustment, an addition of a sulfide source, aeration or a combination of these. Adjusting the pH may involve the addition of sodium hydroxide, limestone, calcium hydroxide, magnesium oxide or a combination of these. Adjusting the pH can be done to result in a pH of approximately 1 to 1.25, approximately 1.25 to 1.5, approximately 5.0 to 5.5 or approximately 5.5 to 6.0. The sulfide source can, for example, be sodium hydrogen sulfide, hydrogen sulphide or a combination of these. In various embodiments, a seed material can be added to the precipitation. In selected modalities, cementation can be done to produce a cement made up of Au, Ag, Cu or a combination of these. In several incarnations, the cementation of Au and Ag can be obtained using, for example, metallic copper. The Ag / Au carburizing solution now free of Ag / Au can then be treated by carburizing iron to remove copper. Thus, a separate precious metal precipitate for refining in a precious metal refinery and a separate copper product are produced. In several modalities, the solution free of iron, silver, gold, copper can then be sent to In / Ga precipitation, raising the pH to produce the
    5/28 In / Ga hydroxide product for further refining. In several embodiments, after removing In / Ga, the solution can be sulfetized with NaSH or other forms of sulfide to precipitate Pb and Zn as separate sulfide concentrates from Pb and Zn. In alternative modalities, precipitation can be made to produce separate products, such as, for example, gypsum and Fe (OH) 3 . Brief description of the drawings [010] Fig. 1 is a diagram showing the leaching of an ore composed of indium, silver, gold, copper, zinc, lead and gallium, followed by recovery of the acid and recycling and recovery of the sequential value in a series of stages, according to a modality of invention. The flowchart also illustrates that, in selected modalities, the solution is treated to remove residual iron and then recycled.
    [011] Fig. 2 is a diagram showing the solvent extraction process to recover, for example, a salt or salts of iron chloride and hydrochloric acid from the heap leach solution according to an embodiment of the invention.
    [012] Fig. 3 is a McCabe-Thiele isotherm, showing the results related to iron cleaning.
    Detailed description of the invention [013] In several respects, the invention provides for an extraction of precious metals, including silver and gold, rare metals, including indium and gallium, base metals, including copper, lead and zinc or a combination of precious, rare and base metals from a complex ore using leaching with oxidizing acid chloride to form leaching or leaching solution. The complex ore can be an oxide ore, a sulfide ore or a combination of oxide ores and the sulfide. In several modalities, the extraction can be followed by a treatment of part or all of the leachate to recover the metal. A selected modality involves the treatment of ores from the Malku Khota ore deposit in Bolivia, which contains various minerals of indium, silver, gold, copper, zinc, lead and other metals. The minerals
    6/28 include a variety of oxides, hydroxides and sulfides.
    [014] In several modalities, the first step in the process involves establishing chemical conditions for the extraction of the metal of interest or a combination of metals. For example, in various embodiments, establishing chemical conditions may involve leaching with acid chloride with an addition of a soluble oxidant. In various embodiments, the soluble oxidant can be, for example, sodium hypochlorite, sodium chlorate, sodium chlorite or a combination of these or other oxidants, such as, for example, chlorine gas, hypochlorous acid (HOCI), Caro acid H2SO5 or a combination of these. In various modalities, the conditions for leaching with oxidizing acid chloride (for example, using sodium hypochlorite) can be selected to produce high extractions of indium, silver, gold, copper, zinc, lead, gallium, other rare, precious metals and basic or a combination of these from complex ores such as oxide ores, sulphide ores or oxide and sulphide ores. In various embodiments, the conditions for leaching with oxidizing acid chloride can be established by mixing, for example, hydrochloric acid (HCl) with a chloride salt (eg. NaCI, KCI, CaCI 2 , MgCI 2 ). The chloride salt adds chloride to the solution to stabilize the dissolved metals as metal chloride complexes. In various embodiments, the conditions for leaching with oxidizing acid chloride can also be established by mixing, for example, sulfuric acid (H2SO4) with a chloride salt. If the chloride salt is NaCI, for example, the resulting mixture can effectively be seen as a mixture of acids and salts HCl, NaCI and Na 2 SO4.
    [015] For example, the leaching of valuable metals in the presence of sodium hypochlorite, according to one embodiment of the invention, can be illustrated by the following simplified chemical reactions in Table 1:
    Table 1
    7/28
    Ιη 2 Ο 3 + 6HCI -> 21nCI 3 + 3Η 2 Ο
    Ag 2 O + 2HCI + 2NaCI 2NaAgCI 3 + H 2 0
    Âg 2 S + 2HCI + NaCI + NaOCl - »2NaÃgCI 2 + S + H 2 O
    Au + 3HCI + 1.5NaOCI NaÃuCU + 1.5H 2 O + 0.5NaCf ”
    CuO + 2HCI »CuCl 2 + H 2 O“ CuS '* 2HQ + NaOCl -> CÜCI 2 + S + NaCI + H 2 Õ
    ZnO + 2HCI '> ZnCI 2 + H 2 O
    ZnS + 2HCI + NaOCl -4 ZnCI 2 + S + NaCI + H 2 O
    PbO + 2HCI f PbCI 2 + H 2 O '''''
    PbS + 2HCÍ + NaOCl -> PbCI 2 + S + NaCI + H 2 O ~ Ga 2 O 3 + 6HCI -> 3GaCI 3 + 3H 2 0 '“[016] In several modalities, it was found that the rate and degree leaching of indium, silver, gold, base metals, rare, or a combination of these is aided by the use of high levels (concentrations) of acid in the solution. For example, the acid level in the solution can vary from approximately 10 g / L to 100 g / L. In the reactions shown in Table 1, acid is a reagent on the left. The consumption of acid in the leaching process is dictated by the acid consumed in the reactions, as shown for examples in Table 1, associated acid consuming reactions, as well as any need for acid neutralization that may be required in some modalities ahead of the recovery steps of the metal. The presence of acid consuming species such as, for example, minerals of iron, aluminum, calcium, magnesium, manganese, antimony, arsenic and other metals is undesirable, as demonstrated by the example reactions simplified in Table 2.
    Table 2
    8/28
    Fe 2 O 3 + 6HCI = 2FeCI 3 + 3H 2 O FeO (OH) + 3HCI = FeCI 3 + 2H 2 O AI 2 O 3 + 6HCI = 2ÁCI3 + 3H 2 O AIO (OH) + 3HCI = AICI3 + 3H 2 O ''
    CaCO 3 + 2HCI = CaCI 2 + CO 2 + H 2 O ~
    MgCO 3 + 2HCI = MgCI 2 + CO 2 + H 2 O
    MnO + 2HCI = MnCI 2 + H 2 O Sb 2 O 3 + 6HCÍ = 2SbCI 3 + 3H 2 O As 2 O 3 + 10HCI + 2NaOCI = 2AsCI 5 + 2NaCI + 5H 2 O [017] The consumption of acid by the species consuming acid such as those shown in Table 2 can be, in some modalities, difficult to avoid and dependent on the minerals present in the raw material, the acid concentration used in the process, the leaching time, the leaching temperature or a combination of these.
    [018] In several embodiments, excess acid can be controlled by employing an acid recovery step. For example, in selected modalities, the Eco-Tec Recoflo process for acid recovery can be used, which employs a bed of strong base ion exchange resin in a thin form to adsorb HCI from the leachate metal. Other acid recovery systems can also be employed in other modalities, including, for example, acid solvent extraction. The adsorbed HCI is then removed using a countercurrent flow of water to allow HCI retention in the leach circuit and to avoid the cost of acid neutralization prior to metal recovery.
    [019] In several embodiments, the formation of, for example, iron chloride salts (s) (eg FeCI 3 ) is generally responsible for a significant component of acid consumption, such as hydrochloric acid ( eg, Fe 2 O 3 + 6HCI = 2FeCI 3 + 3H 2 O) in the process according to the various modalities. In selected embodiments, an extraction solvent process is used to recover, for example, iron chloride acid and salts
    9/28 (eg HCI) from the leach solution (eg stack leach solution).
    [020] According to one embodiment, the solvent extraction process involves loading a kind of iron hydrochloric acid species (eg, iron chloride-hydrochloric acid species such as, for example, HFeCU) into a solvent that comprises a extraction solvent to form a charged solvent In various embodiments, the extraction solvent may comprise, for example, an alkyl phosphate (eg, tri-butyl phosphate (TBP)), an alkyl phosphonate (eg, butyl-butyl phosphonate (DBBP)), an alkyl phosphinate (for example, Cyanex 923) or a combination of these. In various embodiments, the extraction solvent process is selective for FeCF and acid (eg, HCI) over one or more useful metals including chloride species, eg, Ag, In, Ga, Cu, Zn, Pb, Au or a combination of these.
    [021] In several embodiments, the charged solvent (for example, comprising the dilution extractor such as, for example, TBP) is cleaned with, for example, water to form a washed charged solvent. Cleaning with water is similar to washing any species co-extracted from the loaded solvent. In various embodiments, the washed loaded solvent is then removed with additional water (aqueous solution) to displace, for example, FeCh and acid (for example, HCI) in a removal solution.
    [022] In several embodiments, the solution comprising displaced FeCh and HCI is subjected to pre-evaporation to form a pre-evaporated FeCF and HCI solution. This is important to increase the efficiency of the subsequent decomposition process, providing a higher concentration of iron chloride.
    [023] According to various modalities, the removal solution comprising FeCF and acid (for example, HCI) is subjected to thermal decomposition. In several modalities, thermal decomposition can be carried out, for example, by spray roasting, pyrohydrolysis or heating in a
    10/28 decomposing at an appropriate temperature. In various embodiments, the temperature suitable for decomposition can be, for example, 180 ° C or more. Decomposition converts iron chloride into hematite and regenerates the acid (for example, hydrochloric acid) (for example, 2FeCI 3 + 3H 2 0 = Fe 2 0 3 + 6HCI (g); HCl = HCl (gas)).
    [024] In various modalities, the acid (for example, HCl) that is regenerated is condensed and can, for example, be recycled back to the contact stage of the process for the recovery of a metal from an ore, which reduces the general requirement for adding acid to the plant circuit. Fe 2 0 3 (hematite) is recovered as a valuable product.
    [025] According to various modalities, the extraction solvent process also produces a solution low in acid and low in iron. In several modalities, in which the iron has been substantially depleted from the leach solution using, for example, the extraction solvent process, the resulting iron depleted solution (substantially iron-free solution) can be used in the other steps of process in the recovery of valuable metals in accordance with various modalities, examples of which are illustrated in Figure 1.
    [026] In a given embodiment, any residue-free acid in the low iron solution can be neutralized substantially. For example, limestone can be used in a preferred mode. Other neutralizing compounds can be, for example, dolomite, lime, sodium hydroxide or a combination of these.
    [027] After neutralization, in several incarnations, the carburization of Au and Ag can be carried out using, for example, metallic copper, which produces a rich Au-Ag cemented for further refinement. The resulting Ag / Au carburizing solution, which is substantially free of Ag, Au or a combination of Ag and Au, can then be treated by carburizing iron to recover copper. As a result of the processing described above, a separate precipitate of precious metals is formed, which can be used for refining
    11/28 in a precious metal refinery and a separate copper product.
    [028] The resulting solution free of iron, silver, gold, copper can then be sent for In / Ga precipitation, for example, by raising the pH, which produces the In / Ga hydroxide product for further refining.
    [029] After removing In / Ga, the solution can then be sulfidized with, for example, NaSH or other forms of sulfide to precipitate Pb and Zn as Pb as concentrations of Pb and Zn sulfide.
    [030] According to another modality, the recovery of valuable metals from the hydrochloric acid solution (after, for example, the optional recovery of excess acid, using the Recoflo system in selected modalities or other acid recovery methods) you can proceed through a series of steps. Surprisingly, metals can be separated and recovered, for example, as valuable precipitates or cemented using a series of chemical steps. For example, the first step may involve neutralization of excess acid using limestone, for example, CaC03 + 2HCI = CaCÍ2 + C0 2 + H 2 0. In various modalities, the next step may involve reducing precipitation of silver, gold, copper , arsenic or a combination of these with metallic iron. At the same time, in selected modalities, ferric chloride can be reduced to ferrous chloride to prevent or reduce the interference of the ferric ion with the recovery of the Indian by adjusting the pH (Table 3).
    Table 3
    2FeCI 3 + Fe = 3FeCI 2
    2NaAgCI 2 + Fe = 2Ag + FeCI 2 + 2NaCI
    2NaAuGI 4 + 3Fe = 2Au + 3FeCI 2 + 2NaCI ..........
    CuCI 2 + Fe = Cu + FeCI 2
    2CuCI 2 + 2AsCI 5 + 7Fe = 2CuAs + 7FeCI 2 [031] The mixed Ag-Au-Cu-As product can then be processed, for example, using casting / refining tools or hydrometallurgical extraction methods to recover final products of the individual metals.
    [032] In still other modalities, the next stage may be the
    12/28 precipitation of a crude indium hydroxide precipitate by adjusting the pH (Table 4). Aluminum, residual Fe (lll) (if any), chromium, gallium or a combination of these can also be precipitated by adjusting the pH (for example, as shown in Table 4).
    Table 4 lnCI 3 + 3NaOH = ln (OH) 3 + 3NaCI
    ACID 3 + 3NaOH = AI (OH) 3 + 3NaCI ~
    FeClg + 3NaOH = Fe (OH) 3 + 3NaCI “CrCIa + 3NaOH = Cr (OH) 3 + 3NaCI
    GaCI 3 + 3NaOH = Ga (OH) 3 + 3NaCI [033] In several embodiments, the crude indium precipitate can then be processed by a series of acid dissolution / reprecipitation, extraction solvent and electrochemical reduction steps to produce a product of pure Indian and a by-product of gallium. The indium recovery product solution can then be treated by a series of sulfide precipitation measures to form separate or mixed synthetic zinc sulfide and take sulfide concentrates (for example, Table 5).
    Table 5
    ZnCI 2 + NaSH + NaOH = ZnS + 2NaCi + H 2 O PbCI2 + NaSH + NaOH = PbS + 2NaCI + H 2 O [034] In several embodiments, the solution of the final product containing chloride salts can be recycled or disposed of. To return to the process, it is necessary that the iron in solution be removed, which can be carried out, for example, by oxidation and precipitation: 4FeCI 2 + 0 2 + 6H 2 0 + 4CaC0 3 = 4Fe (OH) 3 + 4CaCI 2 + 4C0 2 .
    [035] The extracted ore, which, in various modalities, can contain, for example, indium, silver, gold, copper, zinc, lead, gallium or a combination of these, can be optionally reduced in size before processing. In various embodiments, several wide particle size ranges can be designed to use stack or deposit leaching, leaching in
    13/28 tank, leaching in agitated reactor or a combination of these. For example, in various embodiments, pile or deposit leaching can be performed using compressed material up to a P80 (product size is 80% past the listed nominal size) of approximately 1/8 inch more than approximately 1 inch. Leaching in a stirred reactor can be performed in a size of less than approximately 500 pm (approximately 0.5 mm). In various embodiments, it may be desirable to be thinner in size than approximately 500 pm to reduce potential problems with abrasion. In various embodiments, agitated leaching can be performed at a size of approximately 50 pm. In several other incarnations, tank leaching can be performed using compressed material (and, optionally, ground to the thinnest size range) at a P80 of approximately 0.2 inch (approximately 0.5 mm) more than approximately 1 inch. In various incarnations, compression can be performed without adding water. However, in other embodiments, water jet compression can optionally be used to purify the fine materials formed during the compression operation or a combination of air jet compression and water jet compression. The above methods provide treatment of the fine material separately from the coarse material. In various incarnations, grinding can be carried out without adding water. The addition of water for grinding can be obtained, for example, from fresh water, brackish water, neutral recycling solutions containing chloride or any other available sources.
    [036] In various modalities, ore leaching can be carried out in containers with various configurations, for example, batteries, tanks or in a series of agitated reactors. In certain modalities, leaching of the ore in piles or tanks can be carried out by applying the bleach solution containing acid and the chloride salt. In various embodiments, the acid can be sulfuric acid or a hydrochloric acid with a concentration ranging from approximately 10 g / L to 100 g / L of the acid, and in addition the chloride salt, as
    14/28
    NaCI, can have a concentration ranging from approximately 1 mol / L to 3.5 mol / L.
    [037] In various modalities, the temperature, the extraction time or a combination of these can be modulated. For example, the temperature can vary from the environment (for example, 10 ° C in Bolivia) to the boiling point (which will vary with altitude). In various modalities, the extraction time can vary from days to months to years, depending on the particle size, mineralogy, extraction rate, economics of continuous leaching or a combination of these. In various modalities, leachate obtained from pile or tank leaching can be recovered and directed towards acid recovery or steps in the recovery process. In other embodiments, the leachate ore can be washed in order to recover retained bleach solution containing dissolved metals and residual reagents such as acid and salt chloride. In various embodiments, the leaching of the ore in a stirred tank can be accomplished by mixing the base ore slurry with the acid-containing bleach solution and the chloride salt having, for example, concentration ranges as described above. Upon completion of agitated tank leaching, the leached solids can be separated and washed using, for example, countercurrent thickening and washing, filtration or a combination of these [038] In various embodiments, solids leached by stack, tank or agitated leach can be treated with chemical or physical processes or a combination of chemical or physical processes in order to process materials acceptable for environmental disposal. In various embodiments, the leaching process can also be applied to a concentrate that is recovered from the ore using physical or chemical concentration methods or a combination of chemical or physical methods.
    [039] Leachate obtained from leaching processes in a pile / deposit, tank or agitated tank may contain dissolved metals (for example, indium, silver, gold, copper, zinc, lead, gallium or a combination thereof), residual acid, others chloride salts or a combination thereof.
    15/28 [040] In certain embodiments, the residual acid can be recovered using an acid recovery method such as the Eco-Tec Recoflo system and can be recycled back to the leaching step (for example, as shown in Figure 1). The Recoflo system involves the pre-filtration of fine solids followed by loading and acid elution from an ion exchange resin. The eluate used for this process is water. Therefore, two solution products can be produced from the acid recovery step, a poor acid solution that, in various ways, progresses to metal recovery and neutralization process steps, and an acid recovery solution that, in several modalities, is recycled back to the leaching process. In several other embodiments, the residual acid can be recovered by diverting the acid-containing solution directly to neutralization or using another acid recovery process, such as, for example, solvent extraction.
    [041] In yet another embodiment, the solvent extraction process can be used to recover the iron and acid shown, for example, in Figure
    2. The recovered acid can be recycled and back to the contact step of the process to recover a metal from an ore shown, for example, in Figure 1.
    [042] In several embodiments, the acid-poor solution of the acid recovery process is neutralized to remove excess acid before the carburizing process to recover, for example, silver, gold, copper or a combination of these. In several embodiments, the process may involve the addition of a soluble alkali (for example, NaOH or Na 2 CO3) or a solid alkali (for example, finely crushed limestone or lime). In various embodiments, the pH for neutralization will depend on the temperature and the concentration of various elements in the solution (for example, especially Fe (lll) and Al (lll)). A pH ranging from about 1 to about 1.5 (for example, usually a pH of about 1.25) is suitable for neutralization. In several modalities, the pH can be raised as high as possible without any precipitation of the metal hydroxides
    16/28 of the solution. If limestone or lime is added for pH adjustment, plaster (CaS04.2H 2 0) can be formed if sulfate is present in the solution. If the plaster forms in the neutralization stage, it must be removed and washed before cementation.
    [043] In other modalities, the neutralized solution can be directed to reducing carburization of silver, gold, copper or a combination of these. Iron remnants can be used as a suitable reducer for this step. Alternatively, remnants of aluminum or zinc powder or any other suitable reducer can be used. Reductive carburization can be carried out in a stirred reactor or in a carburizing contactor (eg Kennecott Contactor) to provide sufficient time for the reaction to cure (reduce), silver, gold, copper or a combination of these from the solution. An excess of reducer (in addition to the stoichiometric amount) is necessary to allow an excess of iron in the final product of the cement and to allow for parasitic side reactions (example of hydrogen formation by the reaction of residual acid and reducer and reduction of residual ferric ion (Fe (lll)) for ferrous (Fe (ll))). In various embodiments, the time for reducing carburizing can vary from minutes to hours, and carburizing can be carried out at temperatures of around 10 ° C to the boiling point. The cement product, containing silver, gold, copper and arsenic or a combination of these, can be removed from the solution and washed. The cement product can be treated using various methods currently available. The sterile solution of silver, gold, copper or a combination of these can be developed for the recovery of indium and gallium.
    [044] The recovery of indium and gallium can be carried out in several ways, raising the pH of the solution to the point where the indium and gallium are precipitated. For example, a pH value of about 5.0 to about 6.0 can be used for the purpose of precipitation (the typical value is about 5.5). At this pH, indium and gallium can be recovered from the solution with high efficiency. The precipitate of indium and gallium is recovered from the solution and washed. The precipitate of indium and gallium can then be processed using
    17/28 known methods for obtaining high-purity indium and gallium products.
    [045] In several other modalities, the solution free of indium and gallium is sent to the sulfide precipitation stages. Sulfide precipitation is used to make separate or combined zinc and lead sulfide precipitates for sale or for further treatment. In various embodiments, the sulfide source can be a sulfide chemical (eg, sodium hydrogen sulfide, NaSH) or a sulfide gas (eg, hydrogen sulfide, H 2 S (g)). In several modalities, the sulfide is added to the solution at a controlled rate and, optionally, at a controlled pH (for example, the pH adjustment must be carried out with a soluble alkali, such as NaOH or Na2C03). The sulfide is supplied in a stoichiometric amount to satisfy the chemical requirements for precipitation. ORP (redox potential measured against the Ag / AgCI reference electrode) can be measured during the precipitation process, in order to control the selectivity of precipitation.
    [046] In several embodiments, lead precipitation can be maximized in ORP values from about 100 to about -100 mV (typically, about 0 mV) (measured using an Ag / AgCI ORP electrode). The zinc precipitation then continues to decrease the ORP values (for example, from about -100 to about -300 mV, usually about -200 mV). The pH for the precipitation can be controlled or allowed to vary, depending on the chemistry of the precipitation. If pH control is used, a pH greater than about 1.5 should be targeted. The precipitated lead and zinc sulphides are recovered from the solution separately or together, as a combined product, and can be washed.
    [047] In these other modalities, the zinc and lead-free solution is directed to an iron precipitation stage. Iron precipitation can be conducted with the addition of lime to adjust the pH and aeration for the oxidation of ferrous (Fe (ll)) to ferric (Fe (lll)) for the precipitation and removal of iron from the solution. In several modalities, the pH must be controlled to the maximum values (for example, a pH of about 5 to about 5.5) and must be
    18/28 excess air was supplied in order to oxidize and precipitate the iron from the solution. The iron oxy / hydroxide precipitate can be removed from the solution, washed and discarded. In other embodiments, the iron-free solution can return to the leaching process as a source of soluble chloride.
    [048] In the selected modalities, in cases where there is precipitation, it is advantageous to sow the precipitation, recycling a portion of the solids back to the beginning of the precipitation process. In this way, the precipitate may have the opportunity to grow to a coarser size and become easier to settle, if thickened, or to filter and wash.
    [049] The examples demonstrate the various modalities of the invention, as illustrated in Figure 1, which in addition to the oxidative leaching of acid chloride, shows the additional processing that can be carried out in various modalities in the bleach solution and other process products. The examples further demonstrate the various modalities of the invention in relation to the process illustrated in Figure 2.
    Examples
    Example 1. Acid leaching from the mineral sample containing indium, silver, gold, copper, lead, zinc, gallium [050] A series of six samples designated 08-1 to 08-2 was prepared by grinding to a particle size P80 approximately 50 pm and leach at about 50 ° C in a solution containing about 100 g / L of H2SO4 and about 3 M NaCI. Two methods of adding NaOCI were used. In the first case, a standard of about 1 g / L NaOCI was used for leaching about 35% of the solids content. In the second case, additional NaOCI was added to maintain an ORP of around +950 mV (versus the Ag / AgCI reference electrode). Chemical analyzes of samples 08-1 to 08-6 are shown in Table 6 below. Extractions of acid chloride bleach from samples 08-1 to 08-6 are shown in Table 7.
    Table 6
    19/28
    Element 08-1 08-2 08-3 08-4 08-5 08-6 In (g / t) 5/2 60 ^ .8 89 32 26 Ag (g / t) 135 232 . 777 46 9.91 22-9 Au (g / t) <0.02 0.07 0.03 <0.02 <0.02 <0.02 Cu (g / t) 880 990 1100 95 Ί 65 63 Pb (%) 0.29 Q.17 0.80 0.3 1.09 1 0.67 Zn (g / t) 370 160 690 740 15000 2000 Ga (g / t) <2 7 <2 3 4 4 S(%) 0.03 Q.06 Q.14 0.17 1.05 016
    Table 7
    Sample Addition of NaOCI Method Leaching Time(H) .. ..Extraction (%) In Ag AU Ass Pb Zn Ga 08-1 1 g / L NaOCI 6 58.8 87.608-1 ORP +950 mV 24 69.8 85.8 55.0 94.7 85.4 63.7 26.3 08-2 1 g / L NaOCI 6 15.5 92.908-2 ORP +950 mV 24 32.3 91.9 29.3 46.7 17.0 38.5 9.5 08-3 1 g / L NaOCI 6 41.1 65.008-3 ORP +950 mV 24 60.2 96.9 77.1 90.3 8 ^ .3 55.9 25.2 08-4 1 g / L NaOCI 6 720 87.408-4 ORP +950 mV 24 88.8 81.9 77.1 70.0 58.7 65.8 43.7 08-5 1 g / L NaOCI 6 26.5 45.808-5 ORP +950 mV 24 93.6 95.4 77.3 87.2 95.8 9 ^ .8 8.2 08-6 1 g / L NaOCI 6 40.5 62.408-6 ORP +950 mV 24 77.8 87.1 74.7 91.0 88.2 96.0 31.6
    Example 2. Acid Chloride Stack Leach Accessibility Test [051] Samples 08-1 to 08-6, 09-1, 09-2, 10-1 and 10-2 were subjected to bottle roll tests of acid, using various bleach solutions of grinding solutions and sizes. The chemical analyzes of samples 09-1, 09-2, 10-1 and 10-2 are shown in Table 8. The conditions for the acid bottle roller tests are shown in Table 9. The extractions of chloride bleach Samples 09-1, 09-2, 10-1 and 10-2 are shown in Table 10.
    20/28
    Table 8
    -, ¾. -Element 09-1 09-2 w 10-1 10-2 Λ In (g / t) 12 11 3.2 LO Ag (g / t) 98.5 31.9 108 30.5 Au (g / t) <0.02 0.3 0.02 <0.02 Cu (g / t) 190 40 570 97 Pb (%) 0.36 0.082 0.15 0.16 Zn (g / t) 290 180 1.5 1.4 Ga (g / t) 2 2.9 2.1 3.5
    Table 9
    test Sample Weight(kg) Milling T’C) %Solids ORP(mV) Time(days) Acid(g / L) NaCI.(mol / L) BRL1 08-1 0.5 K80-917 pm 15-25 40 950 14 100- H 2 SO 4 3 BRL2 08-2 0.5 K80-2331 μιτι 15-25 40 950 14 100- H 2 SO 4 3 BRL3 08-3 0.5 K80-1298 pm 15-25 40 950 14 100- h 2 so 4 3 BRL4 08-4 0.5 K80-963pm 15-25 40 950 14 100- H 2 SO 4 3 BRL5 08-5 0.5 K80-325pm 15-25 40 950 14 100- h 2 so 4 3 BRL6 08-6 0.5 K80-398pm 15-25 40 950 14 100- H 2 so 4 3 BRL7 09-1 1 100% -1inch | 15-25 50 950 56 100-HCI 4
    21/28
    BRL8 09-2 1 100% -1inch 15-25 50 950 56 100-HCI 4 BRL9 09-1 1 K80-3 / 8inch 15-25 50 950 56 100-HCI 4 BRL10 09-2 1 K80-3 / 8inch 15-25 50 950 56 100-HCI 4 BRL11 09-1 1 K80-%inch 15-25 50 950 56 100-HCI 4 BRL12 09-1 1 100% - 4mesh 15-25 50 950 56 100-HCI 4 BRL13 09-1 1 100% -10mesh 15-25 50 950 56 100-HCI 4 BRL14 09-1 1 100% - 28mesh 15-25 50 950 56 100-HCI 4 BRL15 10-1 5 K80 - 40 mm 15-25 50 950 56 100-HCI 4 BRL16 10-2 5 K80-40mm 15-25 50 950 56 100-HCI 4
    Table 10
    : · - Test SampleΊ:! 'Extraction (%) 1 In Ag There Cll Pb Zn Ga BRLl 08-1 45 47 46 87 70 26 2 BRL2 08-2 9 53 47 27 8 18 3 BRL3 08-3 27 20 47 82 39 22 2 BRL4 08-4 55 43 46 28 23 18 11 BRL5 08-5 47 70 57 53 42 56 3 BRL6 08-6 20 24 48 33 27 62 1 BRL7 09-1 81 53 23 67 69 71 17 BRL8 09-2 79 34 21 47 99 56 10
    22/28
    BRL9 09-1 86 67 57 83 87 68 25 BRL10 09-2 83 35 57 62 99 61 10 BRL11 09-1 92 59 21 85 91 79 30 BRL12 09-1 92 65 20 84 91 74 33 BRL13 09-1 92 69 24 90 93 83 33 BRL14 09-1 94 78 23 88 93 83 41 BRL15 10-1 76 44 22 78 70 63 11 BRL16 10-2 91 52 19 75 81 60 16
    Example 3. Neutralization of Leachate Acid [052] A sample of the acid chloride leachate was treated with limestone to neutralize the excess free acid before recovery of the valuable metals. The analyzed solution comprised about 9.4 g / L of Fe, about 3.8 g / L of Pb, about 62.5 mg / L of Ag and about 21 mg / L of In. The pH was high to about 1, about 1.5, about 1.75, about 2, about 2.5 using increments of dry powdered limestone. The analysis of the main elements in the solution, depending on the pH for the neutralization of the bleach solution, are shown in Table 11. The temperature of the precipitation was about 21 ° C. The results show that at a pH of about 1.5 and less, iron is not precipitated.
    Table 11
    PH Ensai0 (mg / L) Faith Pb i Ag In Initial 9400 3800 62.5 21 1.00 9500 3700 57 21 1.50 9500 3600 58 22 1.75 9200 3700 56 21 2.00 300 3600 55 20 2.49 22 3300 52 19
    Example 4. Cementation of Ag, Cu and Au [053] A sample of the neutralized leachate (with a pH of around 1.25) was
    23/28 treated with 110% of the iron powder needed to cement the solution's silver, gold and copper, as well as to reduce all iron ions to ferrous ions. This was done at about 21 ° C in a 20 L reactor with 300 rpm agitation. Table 12 shows the analysis of the feed and product solutions and the solid cement recovered from the cementation tests (that is, the initial and final composition of the solution and the composition of the cement). The results indicate a similar quantitative removal of silver, copper and gold from the solution, together with arsenic and antimony. Small amounts of lead, gallium and aluminum were also precipitated.
    Table 12
    Product Amount T Test (mg / L, affl min (ml, g) Faith Fe (ll)Pb Ag Au in Ga Al At Ass Sb Zn Power Solution 14084 8100 71 8029 3800 54.3 0.04 21 0.9 680 82 218 110 320 Fe powderAdded 77 / 100% Product Solution 14114 12000 11600 400 3500 0, B1 0.01 21 0.40 610 921 320 Solid Cement 39.8 442000 21500 18645 148 13D 180 12000 21700 71900 21900 53
    Example 5. In and Ga precipitation [054] A sample of the leachate (after neutralization and cementation) was treated with a solution of 25 g / L of NaOH at 2 ° C at a pH of 5.5 to precipitate the indium and the gallium of the solution. The precipitate of indium and gallium hydroxide was filtered and washed. Table 13 shows the analytical results for the feed and product solutions and the solids from the precipitation of indium and gallium at a pH of 5.5. Indium and gallium are quantitatively precipitated in a similar manner at pH 5.5.
    Table 13
    24/28
    Product / Amount 1 '·· Λ .·· / · ’ Test (mg / L, SÀJ -! - min (ml · g) Faith Fe (ll) Fe (lll) Pb Ag Au In Ga Al At Ass Sb Zn Food 13847 12000 114003800 0β <0.pi 20 1620 6 5 27 330 pH5.S PLS 15148 9900 98203320 <0.p3 <0.02 0.09 | <0.05 <0.9 <3 3.2 <1 291 RES. Final 68 .; 130000 39900 274 NR 5800 I 120 180000 2600 870 5300 6600
    Example 6. Precipitation of Lead and Zinc Sulphides [055] A sample of the solution after the precipitation of indium and gallium at a pH of 5.5 was treated with 50 g / L of NaSH in order to precipitate the sulfide of lead and zinc solution. The ORP and pH of the reaction mixture were monitored with the addition of NaSH. For lead precipitation, a target ORP of 0 mV was defined, after which the lead precipitate was filtered out of the solution. The solution was then treated to a -200 mV target ORP by further adding the NaSH solution. The pH was not controlled. Table 14 shows the analytical results for the feed and product solutions and the solids from the lead and zinc precipitation with NaSH. The synthetic PbS precipitate analyzed 75.4% of Pb with less contamination of the other elements. However, the PbS filtrate still contained 1.31 g / L of Pb. It would be advantageous to add more NaSH to the precipitated lead at a lower concentration before filtering the PbS precipitate. The synthetic ZnS precipitate analyzed 14% of Zn and 61.6% of Pb. This mixed precipitate could be melted for the recovery of these elements in an Imperial Foundry plant.
    Table 14
    Product Amount Assay (mg / L, g / t)(ml, g) Zn Pb Faith Fe (ll) Here Mg Mn At 5 food 12695 291 3320 9900 9820 21000 610 68 77000Filtered from PbS 50 268 1310 1100021000 590 64 70000Filtered from ZnS 14030 1.23 1 950019000 530 57 64000precipitated from PbS 27.2 120 754000 9800200 <20 7 270 12.1 precipitate of ZnS 27.3 140000 616000 24000800 26 13 640 17.3
    25/28 [056] Although various modalities of the invention are disclosed in this document, many adaptations and modifications can be made within the scope of the invention, in accordance with the general knowledge common to those skilled in the art. Such modifications include the replacement of known equivalents for any aspect of the invention to achieve the same result in substantially the same way. Numeric ranges are inclusive of the numbers that define the range. The word comprising is used in this document as any open term, substantially equivalent to the phrase including, but not limited to, and the word comprising has a corresponding meaning. As used in this document, the singular forms one, one and (a) include referents in the plural, unless the context clearly expresses the opposite. So, for example, the reference to one thing includes more than one thing.
    Example 7. The Removal of a Clean, Loaded Organic Solvent for the Recovery of an Iron Chloride and Hydrochloric Acid Solution for the Recovery of Iron and Recycling of the Acid [057] A clean and charged organic solution (100% TBP) was prepared to contain about 40090 mg / L of Fe and about 32.5 g / L of HCl at room temperature. This organic solution was removed with water in an organic to aqueous ratio of about 6: 1 to 1: 4. The aqueous and organic removal solution removed was analyzed for iron and acid concentrations. These values are shown below.
    [058] The results (Table 15 and Figure 3) show that it is possible to recover the iron and acid from the charged organic solvent, using a water removal process. The results of iron removal are shown as a McCabe-Thiele isotherm in Figure 3. This isotherm indicates that it would be possible to remove the charged organic for low residual iron loads in 4 stages at an O / W ratio of 1, 1 to form a removal solution with more than about 40 g / L of Fe. This removal solution would proceed with the recovery of acid and hydrolysis of iron.
    26/28
    Table 15
    Ο / Α ratio Food7 4: 1 .. / .4: 4 Iron Organic ( m 9 / L) 40090 30580 29430 22200 16060 7920 1560Aqueous ( m Q / L) 0 56000 49000 38600 27100 17900 10700 HCI Organic (9 L) 32.5 28 27 24 17 9 0Watery> (Çj / I—) 0 25.0 21.4 19.3 15.6 12.0 8.1
    Example 8. The Initial Boiling of the SX Removal Solution to Concentrate Iron and Acid Levels [059] A solvent extraction removal solution containing about 29.1 g / L Fe (as FeCb) and about 26 , 4 g / L HCI was placed in a glass beaker and reduced in order to concentrate the iron and acid levels in the solution. The evaporated vapor was collected and condensed. The results are shown in Table 16. The condensate contained very little acid (about 4.56 g / L) and was free of any iron content. The concentrated solution that remained after the initial boiling contained about 104.0 g / L Fe and about 77.3 g / HCI, representing a significant concentration of iron and acid species.
    Table 16
    Flow Amount mL Essay g / L / Fe ·· HCI food 3079 29.1 26.4 Condensed 2234 0 4.56 Remaining Solution 878 104.0 77.3
    Example 9. Subsequent Boiling of an SX Removal Solution to Concentrate Iron and Acid Levels and to Form Hematite by Hydrolysis [060] A solution containing about 97.7 g / L Fe and about 80.8 g / L of HCI, representing a solution that had already been pre-concentrated by boiling some of the water in the solution, was then boiled. Water and
    27/28 evaporated hydrochloric acid was collected and condensed. At the end of the test, the reduced solution was very concentrated in iron chloride and acid. To facilitate the recovery of this solution (and the filtration of any solids that have formed by the hydrolysis of iron chloride), a volume of about 420 mL of about 5 g / L of the HCI solution has been added (this solution is called aqueous diluent). The final diluted solution was filtered and the solids collected and analyzed for iron content. The results are shown in Table 17.
    [061] The condensate represented about 2/3 of the original feed solution and contained about 72.3 g / L HCI. This HCI would be available for recycling for the acid leaching process for the treatment of ore. The filtrate was very concentrated in iron (about 236 g / L) and in acid (about 76.2 g / L). A small amount of solids, analyzing about 70% iron, was collected as evidence of iron hydrolysis to form hematite.
    Table 17
    Flow Amount mL Tests q / l Faith HCI food 3000 97.7 80.8 Aqueous Thinner 420 0 5.0 Condensed 2004 0 72.3 Filtered 1305 236 76.2 Residue 6.5 g 70% 0
    Example 10. Subsequent boiling of an SX Removal Solution to Concentrate Iron and Acid Levels and to Form Hematite by Hydrolysis [062] A solution containing about 396 g / L Fe and about 111 g / L HCI , representing a solution that had already been pre-concentrated and partially hydrolyzed by boiling some of the water in the solution, was subsequently boiled. The evaporated water and hydrochloric acid were collected and condensed. At the end of the test, the reduced solution was very concentrated in
    28/28 iron chloride and acid. To facilitate the recovery of this solution (and the filtration of any solids that have formed by the hydrolysis of iron chloride), a volume of about 420 mL of about 5 g / L of HCl solution has been added (this solution is called aqueous diluent). The final diluted solution was filtered and the solids collected and analyzed for iron content. The results are shown in Table 18.
    [063] The condensate represented about 1/3 of the original feed solution and contained about 365 g / L of HCl. This HCl would be available for recycling for the acid leaching process for the treatment of ore. The filtrate was very concentrated in iron (about 467 g / L). A large amount of solids (about 72.5 g), analyzing about 70% iron, was collected as evidence of iron hydrolysis to form hematite.
    Table 18
    Flow Amount mL Essay . g / L Faith HCl food 3001 396 111 Aqueous Thinner 420 0 5 Condensed 1055 0 365 Filtered 2361 467 AT Residue 72.5 g 70% 0
    1/1
    权利要求:
    Claims (17)
    [1]
    1. METHOD FOR RECOVERING A METAL FROM A ORE characterized by the fact that it comprises rare, precious and / or basic metals or a combination of these, the method comprising:
    contacting the ore with an acid, a chloride salt and a soluble oxidant under a selected condition to form an ore residue and an acid-soluble oxidant bleach solution containing the metal;
    the contact of the ore with the leacher involves leaching in pile, leaching in tank, leaching in agitated reactor, mixing or a combination of these, the selected conditions may include a selected temperature, such as room temperature at a boiling point;
    separating the acid-soluble oxidant bleach solution from the ore residue;
    recovering the acid from the acid-soluble oxidant's bleach solution to form a recovered acid and a low-acid bleach solution containing a residual acid, where acid recovery involves: recycling the recovered acid to the contact step; and / or, a solvent extraction including contacting the acid-soluble oxidant bleach solution with a solvent to form a charged solvent having an extracted species, the solvent is an extraction solvent consisting of an alkyl phosphate, a phosphonate of alkyl, an alkyl phosphinate or a combination thereof; and, the separation of the rare, precious and / or base metal from the acid-poor bleach solution in order to recover the rare metal, where the step of separation of the rare metal from the acid-poor bleach solution consisting of: cementation, precipitation or a combination thereof, the precipitation includes one or more of the addition of grain material for the precipitation, a pH adjustment, an addition of a sulfide source, or aeration, the pH adjustment includes the addition of hydroxide sodium, calcium carbonate, or a combination of these so that pH adjustment results in a pH of 1 to 1.25, 1.25 to 1.5, 5.0 to 5.5, or
    5.5 to 6.0.
    [2]
    2. METHOD, according to claim 1, characterized by the fact that
    Petition 870180128384, of 10/09/2018, p. 16/21
    1/1 further comprise neutralization of the residual acid in the acid-low bleach solution by contacting the acid-low bleach solution with a neutralizing agent consisting of calcium carbonate, dolomite, lime, sodium hydroxide or a combination of these to form a solution of neutralized acid-poor bleach.
    [3]
    3. METHOD, according to claim 2, characterized by the fact that the acid-poor bleach solution contains gold and / or silver.
    [4]
    4. METHOD, according to claim 3, characterized by the fact that it further comprises subjecting the acid-neutralized bleach solution to carburizing to produce a gold and / or silver carburized and a carburizing solution.
    [5]
    5. METHOD, according to claim 4, characterized by the fact that the carburizing solution contains copper, and the carburizing solution is subjected to carburizing iron to recover copper to produce a precious metal and a copper product.
    [6]
    6. METHOD, according to claim 5, characterized by the fact that the precious metal is processed by raising the pH, to precipitate indium and gallium to produce an indium and gallium hydroxide, in which the pH is raised from 5.0 to 6.0, typically to 5.5, and a solution low in indium and gallium, and where the solution low in indium and gallium is sulphidized using a sulphide to precipitate lead and zinc as separate sulphide concentrates.
    [7]
    7. METHOD according to any one of claims 1 to 6, characterized by the fact that the ore is an oxide ore, a sulfide ore or a combination thereof.
    [8]
    8. METHOD according to any one of claims 1 to 7, characterized in that the precious metals consist of silver, gold or a combination thereof.
    [9]
    9. METHOD according to any one of claims 1 to 8, characterized by the fact that the rare metals consist of indium, gallium or a combination of these.
    [10]
    10. METHOD according to any one of claims 1 to 9,
    Petition 870180128384, of 10/09/2018, p. 17/21
    1/1 characterized by the fact that the base metals consist of copper, lead, zinc or a combination of these.
    [11]
    11. METHOD according to either claim 1 or claim 10, characterized in that the chloride salt consists of NaCI, KCI, CaCh, MgCh or a combination thereof.
    [12]
    12. METHOD according to any one of claims 1 to 11, characterized in that the soluble oxidant consists of sodium hypochlorite, sodium chlorate, sodium chlorite, chlorine gas, hypochlorous acid or a combination thereof.
    [13]
    13. METHOD according to any one of claims 1 to 12, characterized in that the acid consists of sulfuric acid, hydrochloric acid or a combination thereof.
    [14]
    14. METHOD according to any one of claims 1 to 13, characterized in that the sulfide source consists of sodium hydrogen sulfide, hydrogen sulfide gas or a combination thereof.
    [15]
    15. METHOD, according to any one of claims 1 to 14, characterized by the fact that the precipitation in the step of separation of the rare metal from the acid-poor bleach solution produces a product containing plaster, indium / gallium hydroxide, PbS, ZnS, or Fe (OH) 3 .
    [16]
    16. METHOD according to any one of claims 1 to 15, characterized in that the alkyl phosphate is tri-butyl phosphate or the alkyl phosphonate is di-butyl-butyl phosphonate.
    [17]
    17. METHOD, according to any one of claims 1 to 16, characterized by the fact that the extracted species is a hydrochloric ferroacid chloride species or is HFeCU.
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    同族专利:
    公开号 | 公开日
    MY162992A|2017-07-31|
    US8585991B2|2013-11-19|
    CA2833281C|2020-06-30|
    MX349244B|2017-07-18|
    EP2705168A4|2015-04-29|
    MX2013012774A|2014-03-27|
    AU2012250449A1|2013-11-21|
    BR112013028340A2|2017-06-27|
    CL2013003127A1|2014-04-25|
    CA2833281A1|2012-11-08|
    WO2012149631A1|2012-11-08|
    AU2012250449B2|2017-04-13|
    EP2705168A1|2014-03-12|
    US20120328494A1|2012-12-27|
    CN104379778B|2017-06-16|
    PE20141306A1|2014-09-26|
    CN104379778A|2015-02-25|
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    法律状态:
    2018-01-16| B25D| Requested change of name of applicant approved|Owner name: TRIMETALS MINING INC. (CA) |
    2018-06-12| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2018-10-30| B09A| Decision: intention to grant|
    2019-01-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/04/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161481647P| true| 2011-05-02|2011-05-02|
    US61/481.647|2011-05-02|
    PCT/CA2012/000372|WO2012149631A1|2011-05-02|2012-04-20|A method for recovering indium, silver, gold and other rare, precious and base metals from complex oxide and sulfide ores|
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