WO2014168620A1 - Procédé perfectionné de récupération du plomb et autres métaux à partir de ressources minérales polymétalliques contenant du plomb, et concentré polymétallique composite obtenu par ce procédé - Google Patents

Procédé perfectionné de récupération du plomb et autres métaux à partir de ressources minérales polymétalliques contenant du plomb, et concentré polymétallique composite obtenu par ce procédé Download PDF

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Publication number
WO2014168620A1
WO2014168620A1 PCT/US2013/036148 US2013036148W WO2014168620A1 WO 2014168620 A1 WO2014168620 A1 WO 2014168620A1 US 2013036148 W US2013036148 W US 2013036148W WO 2014168620 A1 WO2014168620 A1 WO 2014168620A1
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Prior art keywords
concentrate
zinc
lead
composite
metals
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PCT/US2013/036148
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English (en)
Inventor
William Leonard LANE
Harold Marion RAY
David Michael OLKKONEN
James Allen JONES
Massimo Giuseppe MACCAGNI
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Metals Technology Development Company, LLC
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Priority to PCT/US2013/036148 priority Critical patent/WO2014168620A1/fr
Publication of WO2014168620A1 publication Critical patent/WO2014168620A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • This invention relates to the recovery of lead and other metals from polymetallic lead-bearing mineral resources, such as ores and tailings, and a composite polymetallic concentrate made there from.
  • polymetallic lead-bearing ores are typically crushed, ground, and separated into individual mineral concentrates (such as a lead concentrate, a zinc concentrate, a copper concentrate, and other mineral
  • a disadvantage of the current methods for the sequential flotation of polymetallic mineral resources into two or more individual mineral concentrates is that there is cross-contamination of the minerals contained in each of the individual concentrates produced ⁇ e.g., a portion of the lead minerals in the mineral resource report to the other individual concentrates), thereby limiting the overall recovery of the metals contained in the complex or polymetallic ores, because these contaminant metals are typically lost in downstream processing.
  • Table 1 shows an example of the distribution of the metals when separate lead, zinc, and copper concentrates are prepared by a sequential flotation process. As indicated in Table 1 , there is cross contamination of metals in the various concentrate, and a significant amount of metal remains in the tailing, and thus is not recovered.
  • the ore body is primarily zinc and lead, and other associated metal values are low
  • the resulting bulk concentrate can be processed, for example according to the Imperial Smelting Process. This is only appropriate for ores of certain compositions, for example where there is more zinc than lead.
  • Embodiments of the present invention provide for the improved recovery of lead, zinc, and other metals from polymetallic mineral resources containing lead, zinc, and other metals, for example from ores containing galena (PbS), sphalerite/blende (ZnS), chalcopyrite (CuFeS 2 ), and additional minerals of value. These additional minerals may include metal compounds that contain lead, zinc, copper, nickel, cobalt, silver, cadmium, and others. Not only do embodiments of the present invention provide increased metal recovery, these methods can also reduce the complexity and ultimately the cost of the milling operation, can reduce the amount of metals that are contained in the final waste product or tailing from the milling process, and can reduce the metal lost in recovery from the resulting concentrates.
  • a method for improved recovery of metals contained in polymetallic mineral resources comprises the production of a composite concentrate consisting of a lead mineral and at least two other metallic mineral compounds.
  • the composite concentrate is prepared to maximize the content of the lead in the concentrate, rather than to minimize the content of contaminating metals. This reduces the inhibiting effect that suppressing contaminating metals has on the recovery of the lead, resulting in more recovery of the lead, and less lead reporting to other concentrates or tailings or other waste.
  • chemical additives or reagents can be added to the flotation process in such a manner as to increase the flotation of other metallic mineral compounds (such as Pb, Zn, Cu, Ni, Co, Ag, Cd, and other metallic mineral compounds) which are further processed by collection, dewatering, and filtering into a final composite concentrate.
  • Additional chemical additives can be added to the flotation process in such a manner to depress a portion of the zinc and/or other compounds contained in ore, for example where it is desired to prepare a separate concentrate of zinc and/or such other metals.
  • these additives are preferably selected, and their quantities controlled, so as not to unduly suppress the flotation the metals that are desired in the composite concentrate, chiefly lead but also including other metals that either cannot be efficiently recovered from a separate concentrate or whose value would otherwise go uncompensated (or even penalized) in a separate concentrate.
  • This suppression of undesirable metals e.g., zinc which can be expensive to recover from a composite concentrate, is balanced against the resulting suppression of other metals, e.g., silver, which would also be suppressed and whose value would be lost in a zinc concentrate or a tailing.
  • Additional zinc can be accepted in the composite concentrate if the additional cost of processing the zinc is less that the value of the additional other metals recovered.
  • a secondary zinc concentrate is prepared. This is because zinc can be efficiently and economically recovered separately, after the flotation of the composite concentrate. A significant portion of the zinc is collected in the composite concentrate because its suppression might unduly suppress the collection and reduce the overall recovery of lead, copper, and silver and other metals.
  • At least one additional flotation process may be used to recover additional zinc compounds into a zinc concentrate.
  • Chemical additives can be added to these flotation processes in such a manner as to increase the flotation of the zinc compounds or other metallic mineral compounds which are further processed by collection, dewatering, and filtering into final concentrate(s).
  • Table 2 shows the metal distribution of a composite concentrate (produced for downstream hydrometallurgical metal recovery), zinc concentrate, and tailing prepared from the same ore as the separate concentrates (typically produced for downstream pyrometallurgical metal recovery) shown in Table 1 .
  • Table 2 shows that a substantial portion of the metals report to the composite concentrate, and that a much lower portion of the metals report to the tailings.
  • Table 3 shows the improved recovery of metals and the reduction of metals reporting to the tailings between the conventional preparation of individual concentrates versus the preparation of a composite concentrate according to the principles of this invention: Table 3
  • the lead can be recovered from the composite concentrate using a Flubor process, developed by Engitec SA, and disclosed in U.S. Patent No. 5,039,337, issued August 12, 1991 , entitled Process for Producing Electrolytic Lead and Elemental Sulfur from Galena, the entire disclosure of which is incorporated herein by reference.
  • a Flubor process developed by Engitec SA, and disclosed in U.S. Patent No. 5,039,337, issued August 12, 1991 , entitled Process for Producing Electrolytic Lead and Elemental Sulfur from Galena, the entire disclosure of which is incorporated herein by reference.
  • lead is leached from the lead concentrate with an acidic aqueous solution of ferric fluoroborate to form ferrous fluoroborate, lead fluoroborate, and elemental sulfur according to the reaction:
  • ferrous fluoroborate and lead fluoroborate circulates to a diaphragm electrolytic cell, where pure lead is deposited at the cathode while at the anode ferrous ion is oxidized to ferric ion.
  • the solution of ferric fluoroborate regenerated at the anode is reused in the leaching step.
  • Sulfur produced by the reaction can be separated from the metal-bearing gangue by extraction with a solvent, or by flotation.
  • the advantages of the Flubor Process include the reduced energy consumption and reduction of slag and S0 2 emissions that are typical by-products of pyrometallurgical recovery processes.
  • the zinc recovered in the process can be recycled for the purification of the solution by precipitation of Pb, Cu, Ni, Co, Ag, and other metals in the form of a cement.
  • some or all these co-products can be processed into separate concentrates that can be added to the initial composite concentrate for processing with the composite concentrate. In other embodiments, some or all of these co-products can be processed into separate concentrates and added to the metal -bearing gangue resulting from the initial lead recovery process, and
  • the solids remaining after the lead leaching and recovery can be processed themselves, or concentrates from the further processing of material remaining after the production of the lead concentrate, can be added before processing.
  • the metals can then be leached from this material with an aqueous- based leaching solution containing chloride ions and ammonium ions, prepared, for example, by dissolving, in water, chlorides of alkaline and/or alkaline-earth metals together with ammonium chloride.
  • the concentration of chloride ions varies within the range of 50- 250 g/l; the concentration of ammonium ions varies within the range of 20-150 g/l.
  • the pH of the solution is neutral, i.e. within the range of 6.5 - 8.5.
  • the leaching is effected under heat, at a temperature varying within the range of 100°C - 160°C, and a pressure varying within the range of 150 kPa-1000 kPa.
  • the duration of the leaching phase varies according to the nature of the solid matrix and the content of metals to be recovered. The leaching typically lasts from one to ten hours.
  • the pH is adjusted to precipitate iron.
  • the pH is further adjusted and the solution is subjected to a sequential cementation recovery in which the addition of less noble metals are used to precipitate more noble metals (Ag, Cu, Pb, Co, Ni, Cd and other metals can be recovered in this manner).
  • a sequential cementation recovery in which the addition of less noble metals are used to precipitate more noble metals (Ag, Cu, Pb, Co, Ni, Cd and other metals can be recovered in this manner).
  • noble metals Al, Cu, Pb, Co, Ni, Cd and other metals can be recovered in this manner.
  • zinc can be recovered from the solution by electrowinning.
  • the metals recovered during the sequential cementation are valuable and readily marketable.
  • the determination of whether to cement the metals separately or in groups is partially a factor of the marketability of the metals in groups versus the economics of separate cementation. It is also a factor of the quantity of the individual metals.
  • the material remaining after the leaching has had most of the metal removed, so that it possibly is no longer considered a hazardous waste in most jurisdictions, and can be used in road and building construction. Having gone through such a severe leaching the comparatively mild leaching used in the TCLP (Toxicity Characteristic Leaching Procedure) testing potentially allows the test to be passed and the waste material to be not hazardous.
  • Table 4 compares the payable metal recovery from a
  • Payable metal recovery refers to the metal values for which the seller is actually compensated, which is less than the actual metal value present, because of various discounts for metal contaminants in the product.
  • the producer would be paid for an additional 9.8% lead, an additional 20.5% zinc, and additional 36.5% copper, and an additional 34.8% silver.
  • the additional metal product not only represents more value recovered, but it also means less metal is present as a contaminant in the resulting tailings, residues and slags.
  • Fig. 1 is a flow chart of a process for the improved recovery of lead and other metals from poly-metallic lead-bearing mineral resources in accordance with the principles of this invention.
  • Fig. 2 is a flow chart showing the preparation of the composite concentrate and secondary zinc concentrate in accordance with the principles of this invention.
  • Fig. 3 is a flow chart of the process for recovering non-ferrous metals from the materials remaining after the recovery of lead according to the process of Fig. 1 .
  • FIG. 1 A preferred embodiment of a process in accordance with the principles of this invention is shown in Fig. 1 .
  • a polymetallic mineral resource containing lead, zinc and other metals e.g., copper, nickel, cobalt, and/or silver
  • these ores contain metals in an oxidized form, more commonly as metal sulfides, such as galena (PbS) and sphalerite (ZnS).
  • PbS galena
  • ZnS sphalerite
  • suppressants to suppress the flotation of other metals such as sphalerite, even at the cost of recovering lead
  • suppressants are only used to the extent that they do not substantially affect the recovery of metals, chiefly lead, desired in the composite concentrate. The result is a greater recovery of lead, which is affected to some extent by the suppressants.
  • other metals such as some of the sphalerite, and various copper, nickel, cobalt, silver metals reporting to the composite concentrate.
  • a lead concentrate is not conventionally formed in this manner because the additional metal values associated with the lead concentrate will not be fully recovered in
  • the resulting concentrate is a composite concentrate, because in addition to increased lead, it has increased amounts of other metals that are usually excluded from a conventional lead concentrate, which, depending upon the source mineral resource, may include zinc, copper, nickel, cobalt, silver, and cadmium.
  • a zinc concentrate may be produced, which in some cases can be efficiently processed using conventional metal recovery techniques, such as a roasting/leaching/electrowinning process.
  • step 24 for the preparation of a composite concentrate is shown in more detail in Fig. 2. After the polymetallic ore is ground and a
  • suppressant such as ZnS0 4 is added to suppress zinc
  • a collector such as xanthate is added to collect sulfides and an iron suppressant, such as NaCN is added to suppress iron (the NaCN addition also has the additional benefit of neutralizing any copper sulfate present in the ore)
  • the ground ore is subjected to a froth flotation separation.
  • a frother such as an aliphatic alcohol is added.
  • Dilution water is added at 104 and the froth containing the lead and other metal values is cleaned, and the composite concentrate is collected.
  • the material that does not float is subjected to a second flotation.
  • a frother such as an aliphatic alcohol is added.
  • An activator such as CuS0 4 is added to promote the flotation of zinc.
  • a collector such as xanthate is added to make the minerals hydrophobic.
  • Dilution water is added and at 108 the froth bearing the zinc is cleaned, and at 1 10 filtered, resulting in a zinc concentrate.
  • This zinc concentrate can be added to the composite concentrate (for example if the other metals in zinc concentrate were more valuable that the additional cost of handling the extra zinc) or, as potentially a better economic alternative, combine it with the residue from the composite concentrate after going through the Flubor process and then taken to the co-product process. In some cases it can be more economically processed using conventional zinc concentrate recovery techniques, such as a roasting/leaching/electrowinning process.
  • the tailing from the Zinc Cleaner Flotation at 108 can have sufficient non-zinc metal values that in addition to a zinc concentrate, a non-zinc metal concentrate may be produced as well. Depending upon the composition of this non-zinc metal concentrate, it can be subjected to the lead recovery process with the composite concentrate. If these non-zinc metal values do not include lead, then some or all of these non-zinc metal values can be can be subjected to a regrinding and flotation, refloated as part of the process of making the composite concentrate, or added to the composite concentrate, for example after the cleaner step and before filtration.
  • tailing from the zinc cleaner flotation at 108 contains zinc, it can be added back to the zinc rough flotation at 106 to recover additional zinc in the zinc concentrate.
  • these non-zinc metal values can be sold for processing by third parties.
  • zinc cleaner tailing or capturing the zinc cleaner tailing and adding directly to downstream processes there may be additional overall achieved metal recovery from the polymetallic resource.
  • the composite concentrate is subjected to a leaching step with an aqueous solution of ferric fluoroborate in fluoroboric acid leaches lead from the composite concentrate.
  • the leachate is separated from the solids which include gangue as well as the other metals, which are not soluble in fluoroboric acid.
  • lead metal is recovered by electrowinning, and the solution is recirculated for leaching of new concentrate.
  • the material remaining after the production of the composite concentrate is subjected to additional flotation and filtering operations to produce one or more concentrates.
  • This will typically include at least a zinc concentrate. What concentrates will be produced will depend upon the content of the starting mineral resource, and the relative prices of the metal constituents, and can include a secondary lead concentrate, a zinc concentrate, and a copper concentrate.
  • Preferably enough of the metal is recovered from the material at step 32, that the resulting tailings can be disposed of without the need for special handling.
  • at least a zinc concentrate is produced which, particularly if it is lead-bearing, can be subjected to a lead recovery process with the composite concentrate in step 26.
  • some or all of the zinc concentrate can be included in the leaching step 26, but if it does not contain lead, it will simply interfere with the operation of the lead recovery steps 26-30, and require a larger system to handle the volume of material.
  • some or all of the zinc concentrate can be included in the further processing of the residuals from the filtering step 28.
  • some or all of the concentrates can be sold for processing by third parties. [0038] It may be that there are sufficient non-zinc metal values in the tailing from the production of zinc concentrate at 32 that in addition to a zinc concentrate, a non-zinc metal concentrate may be produced as well.
  • this non-zinc metal concentrate can be subjected to the lead recovery process with the composite concentrate at 26, as indicated by path 42. If these non-zinc metal values do not include lead, then some or all of these non-zinc metal values can be can be included in the further processing of the residuals from the filtering step 28, as indicated by path 44. Finally, as indicated by path 46 some or all of these non-zinc metal values can be sold for processing by third parties.
  • the solids from the filtering step 28, and any co-product concentrates from the production of the lead concentrate are leached primarily using ammonium chloride NH 4 CI and successively recovering metals from the solution in order of the their electronegativity by additions of zinc, and subsequently
  • the zinc recovered in the process can be recycled for the recovery of other metals, including Pb, Zn, Cu, Ni, Co, Ag, and other metals.
  • the leaching of Additional Metals can be effected with an aqueous-based leaching solution containing chloride ions and ammonium ions, prepared, for example, by dissolving, in water, chlorides of alkaline and/or alkaline- earth metals together with ammonium chloride.
  • concentration of chloride ions preferably varies within the range of 50-250 g/l; and the concentration of ammonium ions varies within the range of 20-150 g/l.
  • the pH of the leaching solution is neutral, i.e., within the range of 6.5 - 8.5.
  • the leaching is preferably effected under heat, at a temperature varying within the range of about 100°C to about 160°C, and a pressure varying within the range of between about 150 kPa and about 1000 kPa.
  • the duration of the leaching phase varies according to the nature of the solid matrix and the content of metals to be recovered.
  • the leaching typically lasts from one to ten hours.
  • the leaching solution comprising chloride ions and ammonium ions, is capable of effectively dissolving the non-ferrous metals of interest, reducing the addition of sulfuric acid and/or sulfates in the leaching solution.
  • the addition of sulfuric acid and sulfate ions can be fact undesired, as, at the end of the extraction process, they generally should be eliminated from the leaching solution (for example, by precipitation in the form of calcium sulfate) with a consequent increase in energy costs, consumption of chemical reagents and production of waste-products to be disposed of.
  • the leaching solution can advantageously contain Cu 2+ ions, introduced, for example, by adding a copper salt such as CuCI 2 . It is believed that the copper ions substantially act as catalyst, favoring the dissolution reaction of the metallic oxides. These ions, in fact, oxidize the sulfides present, reducing in turn the Cu + ions; the Cu + ions are then oxidized again to Cu 2+ by the oxygen present in the reaction environment.
  • a copper salt such as CuCI 2
  • cementation also known as "chemical displacement precipitation”
  • cementation is the reaction through which metals are precipitated in the elemental state, from a solution containing it in dissolved form, by the addition to the solution of another metal in the elemental state (precipitating metal) having a lower (or more negative) reduction potential with respect to the reduction potential of the other metals.
  • Cementation allows the leached metals present in the extraction solution to selectively precipitate separately or in groups, by suitably selecting the precipitating metal on the basis of its reduction potential.
  • the cement obtained generally also contains impurities of one or more of the other leached metals.
  • concentration of these impurities mainly depends on the difference between the reduction potential of the metals which form the impurities and that of the precipitating metal, in addition to the concentration of the respective ions in the solution subjected to cementation.
  • the cement typically contains the main metal precipitated in a highly pure form (higher than 95% by weight with respect to the weight of the cement; the remaining part consists of impurities of other metals in the elemental state).
  • the cements obtained can be re-used as is, or they can be subjected to simple known purification processes, to obtain metals having an even higher purity.
  • the cementation is preferably effected in a plurality of steps in series (multi-step cementation), in each of which one or more of the leached metals precipitates.
  • the precipitating metal is added to the solution subjected to cementation in powder form, thus favoring the chemical displacement reaction which leads to the precipitation of the metallic cement.
  • the precipitating metal is generally added in an excess quantity with respect to that of the metal to be precipitated.
  • the metal added in each of the cementation steps is always the same.
  • the cementation is effected as follows: [0061] Referring to Fig. 3, after the leaching step at A, in a first cementation step at B1 , a first quantity of precipitating metal (for example zinc) is added at 305 to the extraction solution, obtaining the precipitation at 306 of the non- ferrous metal having the highest reduction potential among the metals present in solution (for example silver).
  • a first quantity of precipitating metal for example zinc
  • the precipitating metal is added to the solution in an excess quantity with respect to the metal or metals to be precipitated, so as to cause substantially complete precipitation of the metals to be recovered.
  • the excess precipitating metal (or metals) is calculated in relation to the specific chemical displacement reaction which takes place in the cementation step.
  • the precipitating metal is typically added in an excess of 1 to 50% with respect to the stoichiometric quantity with respect to the metal to be precipitated.
  • the extraction solution is left to decant and the precipitated metal, in the elemental state, is subsequently separated from the supernatant solution, for example by filtration.
  • the precipitation of the second metal e.g., copper
  • the precipitation of the second metal may be accompanied by the possible precipitation of a further quantity of the first metal.
  • supernatant solution 310 can be subjected to a third cementation step at B3, in which a further non-ferrous metal (for example lead) is precipitated at 312 (the one having the highest reduction potential among those still in solution) by the addition of a third quantity of the precipitating metal at 31 1 .
  • a further non-ferrous metal for example lead
  • the precipitation of the cement of the third metal is accompanied by the possible precipitation of increasingly less significant quantities of the previous metals precipitated (silver and copper).
  • the supernatant solution 313 is subjected to possible further cementation steps, such as at B4, similar to the previous steps, until all the non-ferrous metals of interest present in the extraction solution have precipitated and been recovered.
  • at B4 at least one metal (for example nickel and cobalt) are recovered by the addition of a fourth quantity of the precipitating metal at 314.
  • the metal used as the precipitating metal can be any metal having a reduction potential lower than the reduction potential of at least one of the leached metals present in solution.
  • the same precipitating metal is preferably used.
  • the precipitating metal must have a lower reduction potential with respect to the reduction potential of each of the leached metals present in solution.
  • a metal particularly suitable for the purpose is zinc, due to its low cost and greater tendency to oxidize with respect to the non-ferrous metals typically to be recovered.
  • the standard reduction potential of zinc for the pair Zn 2 7Zn is in fact equal to -0.76 V.
  • This cementation process can be used to recover silver, copper, lead, cobalt, nickel, cadmium and other metals more noble than zinc. Typically copper and the silver are recovered together, and the cobalt and the nickel are recovered together.
  • the supernatant solution 313 substantially only contains the ions of the metal used as precipitant in the various cementation steps (in addition to possible residues of ions of non-precipitated leached metals).
  • the supernatant solution can be advantageously subjected to electrolysis to recover the precipitating metal in elemental form, so that it can be re-used in subsequent recovery process cycles or purified and used.
  • the electrolysis of the final extraction solution is preferably effected in an open cell, with a titanium cathode and graphite anode, according to the process described in U.S. Patent No. 5,468,354, Process for Heavy Metal Electrowinning, and U.S. Patent No. 5,534,131 , for Process for Heavy Metal Electrowinning, the entire disclosures of which are incorporated herein by reference.
  • the particular composition of the electrolytic solution which contains CI " and NH 4 + ions, allows the electro-deposition of metallic zinc to be obtained at the cathode and the evolution of gaseous chlorine at the anode. As it is formed, the gaseous chlorine reacts rapidly with the ammonium ions present in solution around the anode forming ammonium chloride with evolution of gaseous nitrogen.
  • the electrolytic process described above is particularly advantageous as it avoids the evolution of gaseous chlorine, which is a toxic gas, in favor of the evolution of gaseous nitrogen.
  • the zinc electro-deposited on the titanium cathode is finally recovered, for example, in the form of a metallic sheet which can be then melted into ingots. Pure zinc powder can be produced from the molten mass.
  • the zinc powder thus recovered can be re-used in new recovery process cycles of non-ferrous metals according to the present invention.
  • Various embodiments of the present invention provide flexibility in handling co-products from the production of the original composite concentrate. In some embodiments, some or all of these co-products can be processed into concentrates that can be added to the composite concentrate for further processing. In other embodiments, some or all of these by-products can be processed with the metal-bearing gangue resulting from the initial lead recovery process.
  • the conditioned slurry (30 - 40% solids) from the mill was placed in a Denver Equipment Co. 500 gram stainless steel flotation cell and operated at 1350 rpm. 5 drops (approximately 0.075 grams/ton) of an aliphatic alcohol frother was added to the flotation cell. The cell was operated for 5 minutes to produce a rougher composite concentrate that was further cleaned in one stage with no additional reagent additions using water addition to dilute the solids. The froth (composite concentrate) was collected, filtered, dried, and processed for analytical assays.
  • a composite concentrate is prepared by flotation separation that contains at least about 85% of the lead, at least about 80% of the copper from the original polymetallic resource and at least 15% but no more than about 50% of the zinc into the composite concentrate.
  • This is in contrast to the prior art where the steps to produce high purity individual concentrates (such as deliberately suppressing recoveries of certain metals) would depress the total recoveries.
  • It is also in contrast to the prior production of bulk concentrates, where zinc would be collected in the bulk concentrate, and not be left in the tail. To achieve this excess xanthates can be used to increase the flotation of lead and copper.
  • Recoveries in the composite concentrate can also be improved by one or more regrinding and flotation steps of the material that does not float to further separate the lead and copper metal from the rock matrix.
  • Suppressants can be used during the flotation separation to suppress the zinc, but preferably not so much that the recoveries of lead and copper are adversely affected.
  • at least about 95 percent, and more preferably 98 percent of the lead is recovered in the composite concentrate, and at least about 90 percent, and more preferably 95% of the copper is recovered in the composite concentrate.
  • At least some of the zinc is present in the composite concentrate, because its suppression can suppress the lead and the copper.
  • the concentrate may have between about 20% and about 70% lead, between about 2% and about 30% zinc, and between about 2% and about 10% copper.
  • the lead content is preferably greater than the zinc content in the composite concentrate.
  • the composite concentrate contains between about 85% and 98% of the lead, between about 20% and about 50% of the zinc, and between about 75% and about 98% of the copper of the polymetallic mineral resource. More preferably the zinc is between 20% and 40% of the composite as a natural (i.e., without additions to specifically enhance or suppress zinc flotation) float.
  • the zinc tailing is preferably processed into a separate zinc concentrate. Sufficient zinc is left in the tail to make this process economic, and to reduce the bulk of the composite concentrate so that the lead can be efficiently and economically recovered.
  • the zinc concentrate can, in some embodiments, be added to the composite concentrate before further processing, but this can unnecessarily increase the size of the system needed for recovering lead to handle the additional volume of material.
  • the zinc concentrate can, in other embodiments be added to the remains of the composite concentrate after the lead has been removed, so that the copper and other metals in the composite concentrate and the zinc (and any other metals in the zinc concentrate) can be recovered in a single process.
  • the zinc concentrate can be processed separately, or sold for separate processing.
  • the lead is conveniently recovered by leaching it with fluoroboric acid according to a Flubor or similar process, and then the leached lead is recovered by electrowinning.
  • the leached metals can be recovered individually, or in groups, including copper, nickel, cobalt, and silver, successively by the introduction of appropriate amounts of less electronegative metals. Different metals can be used for each step, but preferably only zinc is used at least in part because the zinc can be recovered from the leaching solution by electrowinning.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de récupération de métaux à partir d'une ressource minérale polymétallique contenant du plomb, du zinc et autres métaux, le procédé comprenant : séparer par flottation la ressource minérale polymétallique tout en supprimant seulement la flottation du zinc et autres métaux dans une mesure telle que cela n'affecte pas de façon substantielle la flottation du plomb pour former un concentré composite contenant du plomb et un résidu contenant du zinc ; soumettre le concentré composite à un procédé de récupération du plomb dans lequel une solution aqueuse de fluoroborate ferrique dans de l'acide fluoroborique lixivie le plomb à sortir du concentré de plomb, et le plomb est récupéré à partir de la solution par extraction électrolytique ; puis traiter le concentré lixivié pour récupérer au moins un métal supplémentaire.
PCT/US2013/036148 2013-04-11 2013-04-11 Procédé perfectionné de récupération du plomb et autres métaux à partir de ressources minérales polymétalliques contenant du plomb, et concentré polymétallique composite obtenu par ce procédé WO2014168620A1 (fr)

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PCT/US2013/036148 WO2014168620A1 (fr) 2013-04-11 2013-04-11 Procédé perfectionné de récupération du plomb et autres métaux à partir de ressources minérales polymétalliques contenant du plomb, et concentré polymétallique composite obtenu par ce procédé

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PCT/US2013/036148 WO2014168620A1 (fr) 2013-04-11 2013-04-11 Procédé perfectionné de récupération du plomb et autres métaux à partir de ressources minérales polymétalliques contenant du plomb, et concentré polymétallique composite obtenu par ce procédé

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108554618A (zh) * 2018-04-26 2018-09-21 昆明理工大学 一种铜铅锌矿的选矿方法
CN109261345A (zh) * 2018-08-01 2019-01-25 昆明理工大学 一种铜硫矿分离方法
CN110616324A (zh) * 2019-04-11 2019-12-27 苏州重于山新材料科技有限公司 一种利用含银铅锌尾矿提取银及其废渣的利用方法
CN114029158A (zh) * 2021-11-11 2022-02-11 长春黄金研究院有限公司 一种含金银铅锌的多金属矿石选矿工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4385038A (en) * 1980-09-30 1983-05-24 Outokumpu Oy Flotation recovery of lead, silver and gold as sulfides from electrolytic zinc process residues
US4545963A (en) * 1982-09-29 1985-10-08 Sherritt Gordon Mines Limited Process for separately recovering zinc and lead values from zinc and lead containing sulphidic ore
US5074994A (en) * 1990-10-18 1991-12-24 The Doe Run Company Sequential and selective flotation of sulfide ores
US5935409A (en) * 1998-03-26 1999-08-10 Asarco Incorporated Fluoboric acid control in a ferric fluoborate hydrometallurgical process for recovering metals

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4385038A (en) * 1980-09-30 1983-05-24 Outokumpu Oy Flotation recovery of lead, silver and gold as sulfides from electrolytic zinc process residues
US4545963A (en) * 1982-09-29 1985-10-08 Sherritt Gordon Mines Limited Process for separately recovering zinc and lead values from zinc and lead containing sulphidic ore
US5074994A (en) * 1990-10-18 1991-12-24 The Doe Run Company Sequential and selective flotation of sulfide ores
US5935409A (en) * 1998-03-26 1999-08-10 Asarco Incorporated Fluoboric acid control in a ferric fluoborate hydrometallurgical process for recovering metals

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108554618A (zh) * 2018-04-26 2018-09-21 昆明理工大学 一种铜铅锌矿的选矿方法
CN109261345A (zh) * 2018-08-01 2019-01-25 昆明理工大学 一种铜硫矿分离方法
CN110616324A (zh) * 2019-04-11 2019-12-27 苏州重于山新材料科技有限公司 一种利用含银铅锌尾矿提取银及其废渣的利用方法
CN114029158A (zh) * 2021-11-11 2022-02-11 长春黄金研究院有限公司 一种含金银铅锌的多金属矿石选矿工艺
CN114029158B (zh) * 2021-11-11 2023-12-08 长春黄金研究院有限公司 一种含金银铅锌的多金属矿石选矿工艺

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