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    • 专利摘要:
    Metal extraction procedure from ores or polymetallic sulphide concentrates. A process for the extraction of metals from ores or polymetallic sulphide concentrates that comprise at least Cu, Zn, Pb and Ag, which comprises a first stage of atmospheric leaching in sulphate medium in the presence of recycled silver to extract Cu and Zn and a second stage of atmospheric leaching in a chloride medium to extract Pb and Ag. The project leading to this application has received funding from the European Union's Horizon-2020 research and innovation program under grant agreement No. 689515. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2794298A1
    申请号:ES201930435
    申请日:2019-05-17
    公开日:2020-11-17
    发明作者:Gómez Carlos Frías；Ruíz Francisco Sánchez；Avilés Jorge Antonio Blanco
    申请人:Cobre Las Cruces S A U；
    IPC主号:
    专利说明:

    [0002] Metal extraction procedure from ores or polymetallic sulphide concentrates
    [0004] A process for the extraction of metals by hydrometallurgy from minerals or polymetallic sulphide concentrates that contain various base metals and precious metals, and which comprise at least Cu such as chalcopyrite, Zn, Pb and Ag, and which comprises a first stage of leaching at atmospheric pressure, in a sulfate medium and in the presence of silver in an ideal quantity to catalyze the leaching of copper and zinc, and a second stage of leaching at atmospheric pressure and in a chloride medium, where lead and silver are leached; these four metals are subsequently recovered separately as high-value products.
    [0006] The project leading to this application has received funding from the European Union's Horizon-2020 research and innovation program under grant agreement No.
    [0007] 689515.
    [0009] Background of the invention
    [0011] There are numerous copper, zinc or lead smelters or refineries in the world that treat concentrates of Cu, Zn or Pb sulphides individually; It can be said that they are "mono-metallic" type refineries. There are also ISF type smelters ("Imperial Smelting Furnace") that jointly treat Zn and Pb sulfide concentrates. However, to date there is no industrial refinery of the "poly-metallic" type capable of treating polymetallic concentrates containing copper, zinc and lead sulphides all of them together in a global concentrate of Cu, Zn and Pb, which also contains silver, that is to say, containing the four metals Cu, Zn, Pb and Ag, to jointly valorize them in the same raw material. One of the objectives of this invention is precisely to promote the concept of a "poly-metallic" refinery capable of treating global concentrates and recover the four aforementioned metals in the same refinery. Additionally, other minority metals could also be recovered.
    [0013] The extraction of metals from ores or polymetallic concentrates is difficult and complex because it is required to efficiently and feasibly separate and recover various metals in an integrated process in situ, thus obtaining refined metals of high value from These polymetallic raw materials require an efficient combination of many process steps, which is very complicated and expensive because reactors operating at high pressures and temperatures are usually used, particularly when the copper is in the form of chalcopyrite.
    [0015] The Spanish patent document with publication number ES0476055A1 describes the extraction of Cu, Pb, Zn, Ag and Au from complex sulfur minerals (containing chalcopyrite), by means of a procedure that comprises a pressure reactor with oxygen, operating at 200 ° C, where all metal sulfides are oxidized to sulfates, subsequently recovering the various metals separately.
    [0017] Likewise, the Spanish patent document with publication number ES8607418A1 describes the extraction of Cu and Zn and the recovery of Pb and / or precious metals from zinciferous sulphurous materials, by means of a two-stage leaching procedure, the first operating in reactor under pressure and a temperature of 120-160 ° C, and the second at a temperature below the boiling point and under atmospheric pressure conditions.
    [0019] Also, in the Spanish patent document with publication number ES2137871A1 the extraction of Cu, Pb, Zn and Ag is described from polymetallic sulphide minerals of iron and other non-ferrous metals, and especially, of pyritic-based minerals containing smaller amounts of Cu sulphides (such as chalcopyrite), and of Zn, Pb and Ag, by means of a hydrometallurgical process that combines oxidation operations in aqueous medium with oxygen in a reactor at pressure and at a temperature of 220 ° C.
    [0021] Patent document number US3856913A proposes a procedure for bioleaching in agitated tanks with aeration of minerals or concentrates containing chalcopyrite in a sulfuric acid medium where a soluble silver salt of the nitrate, sulfate or chloride type is added in a proportion greater than 200 mg Ag (I) per kg of mineral or concentrate. Also, patent number AU7856098A proposes a procedure for bio-leaching in heaps of minerals containing chalcopyrite with a previous stage of agglomeration of the mineral adding an acid solution containing a silver salt in a proportion of 10-500 mg Ag (I) per kg of mineral.
    [0023] In the same way, the Japanese patent document JP2013173962A describes a process to leach chalcopyrite concentrates by contacting said concentrate together with agglomerated particles in a stirred tank at a temperature below 80 ° C. of silver sulfide or chloride much larger than that of the concentrate and which are prepared by pressing said silver salts forming a kind of pellets; subsequently, the leached pulp is screened and the silver agglomerates are recovered and recycled to the leaching. In any case, there is loss of a certain amount of silver due to wear or abrasion of the aforementioned agglomerates.
    [0025] In another US patent US2013209335A1 a method is proposed to recover copper from chalcopyrite concentrates by putting the concentrate in contact in a stirred reactor together with another pyrite concentrate that has been previously conditioned by adding silver salts in a proportion greater than 50 mg Ag (I ) per kg of concentrate; At the outlet of the reactor, the pyrite is separated from the leached pulp by some gravimetric method and it is recycled back to the leaching. In this case, some of the silver adhering to the pyrite concentrate may be lost due to abrasion and because some of the pyrite concentrate will not be recoverable.
    [0027] After the leaching stage, in order to recover and recover in an integrated way the various metals such as Cu, Zn, Pb and Ag contained in the minerals or polymetallic sulphide concentrates, an ideal combination of various techniques is required and, on the other hand, it is necessary employ different chemical media such as sulfate medium, chloride medium, etc.
    [0029] In relation to the above, patent document number ES0476055A1 describes a process for recovering copper and zinc dissolved after pressure leaching in an autoclave by means of solvent extraction and electrolysis, while lead and precious metals are put into solution in a concentrated medium of chlorides and then recovered by cementing with zinc.
    [0031] Another patent document with publication number WO2015044353 describes the atmospheric leaching of a metallurgical residue containing silver and lead in the presence of chlorides and with an oxidizing agent, and subsequently, a carbonate salt is added and lead and silver are recovered as a carbonate concentrate.
    [0033] On the other hand, the patent with publication number WO2015178752A1 proposes to recover lead and precious metals from secondary raw materials by leaching in a solution rich in sodium sulfide that converts lead sulfate into a lead sulfide concentrate accompanied by silver and gold.
    [0034] It can be understood that treating minerals or polymetallic sulfide concentrates to be able to recover in situ various metals such as Cu, Pb, Zn and Ag efficiently and obtaining high purity products is still a challenge for the metallurgical industry that it is necessary to develop because these materials Polymetallic and complex raw materials are increasingly abundant in nature, as the better quality mineral deposits are gradually depleted. The in situ treatment of polymetallic minerals also has other advantages, including environmental ones, since it is not necessary to produce and transport metallic concentrates to be treated in refineries located at great distances from the mine where said concentrates are obtained.
    [0036] Description of the invention
    [0038] As mentioned above, there are different processes to treat global concentrates containing various metals to be recovered (among them copper in the form of chalcopyrite) based on the use of high pressure reactors (autoclaves) and which present certain limitations: on the one hand, the Investment and operating costs are very high and, on the other hand, a huge amount of gypsum is generated due to the complete oxidation of sulfides to sulfates. However, no process has been proposed that allows treating global concentrates, mostly containing copper as chalcopyrite, working at atmospheric pressure, thus avoiding the limitations of pressure reactors; This new concept of process capable of effectively treating global concentrates containing Cu as chalcopyrite and Zn, Pb and Ag in the form of sulfides at atmospheric pressure and with low investment and operating costs and minimal oxidation of sulfides is one of the objectives of the present invention.
    [0040] Processes that work at atmospheric pressure have also been previously described to benefit copper concentrates in the form of chalcopyrite by adding silver salts that act as a catalyst to leach the chalcopyrite; However, until now the catalytic effect of silver has not been applied to global or polymetallic concentrates containing Cu as chalcopyrite and Zn, Pb and Ag in the form of sulfides, whose individual behavior may be different for each of these metals, being another Objective of the present invention to define how to use the catalytic effect of silver to optimize the leaching of both metals, copper and zinc.
    [0042] Probably, processes based on the extraction of copper (in the form of chalcopyrite) by adding a silver catalyst have not had industrial application until now due to economic factors, as there may be significant losses of silver that was not recovered. With the present invention this drawback is solved, since the proposed hydrometallurgical process allows the four metals Cu, Zn, Ag and Pb to be fully recovered.
    [0044] Thus, the problem solved by the present invention is the recovery and valorization of Cu, Zn, Pb and Ag present in minerals or polymetallic sulphide concentrates, substantially improving the existing high pressure leaching processes in autoclaves that are complex and expensive; In this sense, a silver-catalyzed atmospheric pressure leaching is proposed, which is fully recovered and can be recycled to the process itself.
    [0046] Another purpose of the present invention is to provide a hydrometallurgical process that allows the recovery of copper, zinc and lead metals as refined metals of high purity, and silver as a metallic product (in the form of silver cement) of high commercial value. .
    [0048] The use of the silver catalyst increases the extraction of the sum Cu and Zn.
    [0050] Other purposes of the present invention that allow significant savings and make this new hydrometallurgical process more economically attractive; On the one hand, a fraction of the silver cement produced, which has optimal catalytic properties, can be recycled in a suitable quantity to catalyze the leaching of copper and zinc; On the other hand, a part of the lead produced can also be recycled to cement silver.
    [0052] Other purposes and advantages of the present invention are shown and will be understood from the following description and from the figures and examples presented below for purposes of illustration and not limitation.
    [0054] Therefore, a first aspect of the invention refers to a process for the extraction of metals from minerals or polymetallic concentrates, comprising Cu sulphides in the form of chalcopyrite and Zn, Pb and Ag sulphides, comprising the steps of :
    [0055] a) A first stage of leaching at atmospheric pressure, in sulfate medium, of the initial raw material: minerals that comprise Cu sulphides, in the form of chalcopyrite, and Zn, Pb and Ag sulphides or polymetallic concentrates that comprise Cu sulphides in form of chalcopyrite, and sulfides Zn, Pb and Ag, in the presence of oxygen and ferric sulfate, with addition sulfuric acid and a silver catalyst to obtain a solution rich in Cu and Zn and a leached solid containing Pb and Ag as sulfates;
    [0056] b) separation of the solution rich in Cu and Zn and the leached solid containing Pb and Ag from step a) above, in the form of a leached residue of precipitated Ag and Pb sulfates; c) extraction of Cu by adding a specific organic extractant for copper to the solution rich in Cu and Zn, to obtain a purified solution loaded with Cu and an exhausted raffinate containing Zn;
    [0057] d) obtaining Cu by electrodeposition from the purified and loaded Cu solution obtained in step c);
    [0058] e) elimination of the Fe present in the spent raffinate from step c) above by precipitation through the oxidation of Fe (II) to Fe (III) and pH adjustment between 3 and 4, obtaining a solution loaded with Zn and free of iron and an iron precipitate, part of the iron precipitate is recycled to the leaching step a) to provide and maintain the required Fe (III) concentration;
    [0059] f) Purification and concentration of the Zn-loaded and iron-free solution of step e) by adding a specific organic extractant for zinc to the Zn-loaded solution, to obtain a purified and Zn-loaded solution and a refining containing residual zinc that is recycled to step a) above;
    [0060] g) obtaining Zn by electrodeposition from the purified and charged Zn solution;
    [0061] h) second stage of atmospheric leaching of the leached residue comprising Pb and Ag from stage b) in a saturated water solution of a chlorine salt at a temperature between 60 ° C and 100 ° C, giving rise to a Ag and Pb loaded solution; j) recovery of Ag, from the solution loaded with Ag and Pb by reducing it with lead metal, recycling from step k) below, to form an Ag cement and a solution enriched in Pb; part of the silver cement produced is recycled as a catalyst to stage a);
    [0062] k) recovery of Pb from the Pb-enriched solution by chemical reduction adding metallic aluminum, to form a lead cement and a spent solution that is recycled to step h) of this process; a part of the lead produced is recycled to stage j) to cement the silver.
    [0064] Brief description of the drawings
    [0066] For a better understanding of what has been exposed, some drawings are attached in which, schematically and only as a non-limiting example, a case is represented practical realization.
    [0068] Figure 1 is a diagram of the process of the invention including all the stages of the process, as described in the following section, and detailed in Example 1.
    [0070] Figure 2 is another diagram of the process of the invention including all the stages of the process, and detailed in example 2.
    [0072] Detailed description of the invention
    [0074] As has been said, a first aspect of the invention refers to a process for the extraction of metals from minerals or polymetallic concentrates, comprising Cu sulphides in the form of chalcopyrite and Zn, Pb and Ag sulphides, comprising the steps of :
    [0075] a) A first stage of leaching at atmospheric pressure, in sulfate medium, of the initial raw material: minerals that comprise Cu sulphides, in the form of chalcopyrite, and Zn, Pb and Ag sulphides or polymetallic concentrates that comprise Cu sulphides in form of chalcopyrite, and sulfides Zn, Pb and Ag, in the presence of oxygen and ferric sulfate, with the addition of sulfuric acid and a silver catalyst to obtain a solution rich in Cu and Zn and a leached solid containing Pb and Ag as sulfates;
    [0076] b) separation of the solution rich in Cu and Zn and the leached solid containing Pb and Ag from step a) above, in the form of a leached residue of precipitated Ag and Pb sulfates; c) extraction of Cu by adding a specific organic extractant for copper to the solution rich in Cu and Zn, to obtain a purified solution loaded with Cu and an exhausted raffinate containing Zn;
    [0077] d) obtaining Cu by electrodeposition from the purified and loaded Cu solution obtained in step c);
    [0078] e) elimination of the Fe present in the spent raffinate from step c) above by precipitation through the oxidation of Fe (II) to Fe (III) and pH adjustment between 3 and 4, obtaining a solution loaded with Zn and free of iron and an iron precipitate, part of the iron precipitate is recycled to the leaching step a) to provide and maintain the required Fe (III) concentration;
    [0079] f) Purification and concentration of the Zn-loaded and iron-free solution of step e) by adding a specific organic extractant for zinc to the Zn-loaded solution, to obtain a purified and Zn-loaded solution and a refining containing residual zinc that is recycled to step a) above;
    [0080] g) obtaining Zn by electrodeposition from the purified and charged Zn solution;
    [0081] h) second stage of atmospheric leaching of the leached residue comprising Pb and Ag from stage b) in a saturated water solution of a chlorine salt at a temperature between 60 ° C and 100 ° C, giving rise to a Ag and Pb loaded solution; j) recovery of Ag, from the solution loaded with Ag and Pb by reducing it with lead metal, recycling from step k) below, to form an Ag cement and a solution enriched in Pb; part of the silver cement produced is recycled as a catalyst to stage a);
    [0082] k) recovery of Pb from the Pb-enriched solution by chemical reduction adding metallic aluminum, to form a lead cement and a spent solution that is recycled to step h) of this process; a part of the lead produced is recycled to stage j) to cement the silver.
    [0084] Silver is recycled from the process itself, so an autoclave is not required and only a controlled part of the sulfides is oxidized to sulfate, leaving the rest as elemental sulfur, and it is also possible to recover and recycle 100% of the silver used as a catalyst .
    [0086] In the present invention, when "silver cement" is mentioned, it refers to a product that is obtained by chemical reduction of silver from the rich solution of Pb and Ag of step h) with a metal with an oxidation potential greater than silver. (M1), so that silver is deposited on the metal, added in a certain excess, and a metallic product is formed that contains Ag (0) and a certain residual portion of the other metal M1. Therefore, silver cement is a A metallic product that basically consists of Ag (0) and a metal with an oxidation potential greater than silver.
    [0088] In the present invention, when "lead cement" is mentioned, it refers to a product obtained by chemical reduction of lead from the solution enriched in Pb of step i) with a metal with an oxidation potential greater than lead (M1) , so that lead is deposited on the metal, added in a certain excess, and a metallic product is formed that contains Pb (0) and some residual portion of the other metal M1. Therefore, lead cement is basically a metallic product consisting of Pb (0) and a metal with a higher oxidation potential than lead.
    [0090] In the present invention, when "specific organic extractant for Cu" is mentioned, it refers to a reagent whose main characteristic is its high selectivity for extracting Cu in step c). In particular, the specific organic extractant for Cu is selected from hydroxy oximes, ketoximes, aldoximes and mixtures thereof.
    [0092] In the present invention, when "specific organic extractant for Zn" is mentioned, it refers to a reagent whose main characteristic is its high selectivity for extracting Zn in step f). In a particular case, the specific organic extractant for Zn is an organophosphoric acid.
    [0094] The extraction with solvents of Cu and Zn is carried out by means of liquid-liquid contact between the aqueous solution containing these metals and a specific organic solvent, being an ion exchange process, passing protons from the organic phase to the aqueous phase and the Cu (II) or Zn (II) ion from the aqueous phase to the organic phase in a selective way according to the conditions in which these processes are carried out. Solvent extraction techniques have two fundamental objectives, purify and concentrate Cu or Zn in preparation for steps d) and g) of the respective electrodeposition of these metals.
    [0096] In the present invention, when "polymetallic sulfide minerals or concentrates" are mentioned, it refers to mineral raw materials that are mainly composed of iron sulfide (pyrite), copper sulfides (chalcopyrite, chalcosine, covellin, etc.), zinc sulfide. (blende or sphalerite) and lead sulfide (galena) along with other minor elements such as Ag, Au, etc.
    [0098] In the present invention, when “enriched air” is mentioned, it refers to enriched air that has between 30% and 80% oxygen, it is generally obtained by simple mechanical equipment, by means of air filtration through membranes.
    [0100] Preferably, in the process of the invention, stage a) is carried out in two successive sub-stages, the first sub-stage without adding the silver catalyst and the second sub-stage adding the silver catalyst, keeping the rest of the conditions as to what has already been described for stage a). With this stage, a more efficient leaching of the sum of the two metals Cu and Zn is achieved, as can be seen in Example 2 below.
    [0102] Preferably, in step a), chloride ions are added in the form of a salt until a concentration of more than 0.4 g / l of chloride ions is reached in the leaching solution. Particularly sodium chloride. As can be seen in Example 3 the addition of ions Chloride along with the silver catalyst increases the leaching of zinc.
    [0104] Preferred materializations of stage a) of atmospheric leaching in sulfate medium of the raw material are the following:
    [0105] ■ the particle size of the raw material is equal to or less than the degree of release required for the mineral species of the sulphides of Cu, Zn, Pb and Ag. Preferably, this size is between 10 and 100 microns;
    [0106] ■ Preferably step a) of leaching is carried out in leaching reactors. The temperature of the leaching reactors is between 80 ° C and 100 ° C. The residence time in the leach reactors is between 6 hours and 24 hours.
    [0107] ■ added sulfuric acid is in a range between 20g / l and 100g / l
    [0108] ■ The concentration of Fe (III) ion present as ferric sulfate is in a range between 5g / l and 50g / l.
    [0109] ■ Oxygen is injected into the bottom of the reactors at a pressure of 6 bar.
    [0110] ■ The dose of silver depends on the nature and mineralogy of the mineral raw materials. For the treated raw materials, it is required to add silver in a proportion that usually varies between 250 and 1000 grams of Ag per ton of solid raw material.
    [0112] In a preferred embodiment of step b) of solid / liquid separation, the pulp that comes out of step a) is cooled in pulp cooling towers, and then the cold pulp enters a thickener where the two streams are separated, through the Overflow, the rich solution of Cu and Zn flows to the next stage, while the leached residue containing Pb and Ag is extracted from the bottom and sent to filtration and washing, recovering in filtered liquor, which returns to the thickener.
    [0114] In preferred embodiments of stages c) and d) of selective extraction of copper with organic solvent and its electrodeposition:
    [0115] ■ The organic extractant is a mixture of aldoxime and ketoxime.
    [0116] ■ The operating temperature is in the range of 35 ° C to 40 ° C.
    [0117] ■ The copper solvent extraction circuit consists of three in-line process steps: extraction, washing, and re-extraction. During the extraction, the organic extractant is brought into contact with the solution rich in Cu and Zn to obtain an organic phase loaded with copper and an aqueous solution that is poor in copper and enriched in sulfuric acid, called aqueous refining, which passes to the next stage.
    [0118] ■ The organic phase is washed where it comes into contact with water at an acid pH and certain impurities are eliminated, such as iron, chlorides, etc.
    [0119] ■ The washed organic phase passes to copper re-extraction and is put in contact with an acid solution (exhausted electrolyte) from copper electrolysis to obtain a copper-depleted organic phase that returns to extraction and a copper-rich aqueous solution that passes to copper electrodeposition.
    [0120] ■ Highest purity grade 1 copper cathodes are produced.
    [0122] Preferred embodiments of step e) of iron removal are:
    [0123] ■ The operating temperature is between 35 ° C and 40 ° C.
    [0124] ■ The residence time in iron neutralization and precipitation reactors can vary between 2 hours and 5 hours.
    [0125] ■ As a neutralizing agent, calcium hydroxide is added until reaching a pH between 3 and 4. Optionally, primary materials such as zinc calcines or secondary materials such as Waelz oxides can be added as alkali.
    [0126] ■ The objective of this process is to eliminate and precipitate the maximum of the iron that is dissolved, and a purified solution rich in zinc and containing less than 10 ppm of Fe is obtained, which passes to the next stage.
    [0127] ■ milk of lime or limestone or zinc oxides is added, and the following is injected: air, enriched air or oxygen
    [0129] In a preferred embodiment of steps f) and g) of selective extraction of zinc with organic solvent and its electrodeposition, the processing conditions are:
    [0130] ■ The organic extractant is di (2-ethylhexyl) phosphoric acid.
    [0131] ■ The operating temperature is in the range of 35 ° C to 40 ° C.
    [0132] ■ In particular, the zinc solvent extraction circuit consists of four in-line process steps: extraction-1, extraction-2, washing and re-extraction. In extraction-1, the organic extractant is put in contact with the solution rich in Zn to obtain an organic phase loaded with zinc and an aqueous solution with a low concentration of zinc and enriched in sulfuric acid, called aqueous refined-1, which becomes the extraction stage-2 once the raffinate-1 has been conditioned with calcium hydroxide to neutralize the sulfuric acid contained. After the extraction stage-2, an organic phase more loaded with zinc and an aqueous acidic solution depleted in zinc, called raffinate-2, are obtained, which is recirculated to Stage a) of leaching, thus closing the extraction plant circuit of Cu and Zn.
    [0133] ■ The organic phase is washed where it comes into contact with acidified water and is they eliminate certain impurities, such as calcium, chlorides, etc.
    [0134] ■ The washed organic phase goes to re-extraction of zinc and is put in contact with an acid solution (exhausted electrolyte) from zinc electrolysis to obtain an organic phase depleted in zinc that returns to extraction-1 and an aqueous solution rich in zinc which happens to electrodeposition of zinc.
    [0135] ■ The highest purity zinc cathodes are produced, suitable for making commercial SHG grade zinc ingots.
    [0137] In preferred materializations of stage h) of atmospheric leaching in the chloride medium of the solid residue that comes from stage b) and contains lead and silver sulfates are: ■ Temperature of the leaching reactors between 60 ° C and 100 ° C .
    [0138] ■ Residence time in the leaching reactors between 1 hour and 3 hours.
    [0139] ■ The chloride concentration ranges from 1.5 to 4.5 N.
    [0140] ■ The added acid can be sulfuric or hydrochloric and the necessary acid is added until reaching a pH between 0.2 and 4.0.
    [0141] ■ In the treated raw materials, a leaching or dissolution efficiency of lead is higher than 95%.
    [0142] ■ The efficiency of silver leaching or dissolution depends on the mineralogy and silver grade in the original raw material, and also depends on the amount of silver added as a catalyst in Step a). In the treated raw materials, a silver leaching or dissolution efficiency is reached higher than 96%, recovering in any case 100% of the silver added as a catalyst to stage a) plus a certain percentage corresponding to the silver contained in the original raw material.
    [0143] ■ in step h) other metals with a lower electrode potential than lead can be added.
    [0145] In a preferred embodiment of stage j) of silver recovery by chemical reduction, metallic lead from stage l) is recycled and brought into contact with the silver-loaded solution, obtaining a silver cement powder. Part of this cement is recycled in step a). The processing conditions are:
    [0146] ■ Temperature of silver cementation reactors between 60 ° C and 80 ° C.
    [0147] ■ Residence time in silver cementation reactors comprised between 0.25 hour and 1 hour.
    [0148] ■ in step j) other metals with a lower electrode potential than silver can be added.
    [0149] In a preferred embodiment of step k) of recovery of lead by chemical reduction, metallic aluminum is used, which is brought into contact with the lead-laden solution, obtaining a lead cement powder. This lead dust is compacted and subsequently melted in stage l) to obtain lead ingots as a final product. Part of the lead produced is recycled in step j). Preferably the processing conditions are:
    [0150] ■ Lead cementing reactors temperature between 60 ° C and 80 ° C.
    [0151] ■ Residence time in lead cementing reactors comprised between 0.25 hour and 1 hour.
    [0153] Preferably, the metal extraction process proposed in the present invention from minerals or polymetallic sulphide concentrates and which comprises at least the metals Cu, Zn, Pb and Ag is illustrated in a simplified way in the diagram of the Figure 1 and comprises the following main stages:
    [0155] Such stage. Atmospheric leaching in sulfate medium
    [0157] Atmospheric leaching in hot aqueous medium of the raw material (1) once ground to a particle size where the sulfur minerals of Cu, Zn, Pb and Ag are released and accessible for their chemical reaction in the presence of oxygen and with the addition of sulfate ferric and sulfuric acid, and adding a catalyst consisting of a silver cement obtained and recycled from Stage [j] in order to achieve efficient leaching and obtain a leached solid (3) that passes to the next stage within the stream (2) of leached pulp. The main reactions that occur in this stage of atmospheric leaching are:
    [0158] (i) CuFeS 2 + 2 Fe2 (SO4) 3 = CuSO4 5 FeSO4 2 S °
    [0159] (ii) ZnS Fe 2 (SO 4) 3 = ZnSO 4 + 2 FeSO 4 + S °
    [0160] (iii) PbS Fe 2 (SO 4) 3 = PbSO 4 (s) 2 FeSO4 S °
    [0161] (iv) Ag 2 S Fe 2 (SO 4) 3 = Ag 2 SO 4 (s) 2 FeSO 4 + S °
    [0162] (v) 2 FeSO 4 + 0.5 O 2 + H 2 SO 4 = Fe 2 (SO 4) 3 + H 2 O
    [0164] Reactions (i) and (ii) are catalyzed by the presence of silver added as silver cement. In reactions (iii) and (iv), lead and silver sulfates are formed in solid form, and are incorporated into stream (3). Reaction (v) occurs simultaneously with the previous ones, continuously regenerating the necessary Fe (III) sulfate so that reactions (i) to (iv) progress in an effective way.
    [0166] Stage [b !. Solid / liquid separation in leached copper and zinc pulp
    [0168] Separation of the leached solid residue (3) and a solution rich in Cu and Zn (4) using conventional thickening and filtration equipment.
    [0170] Stage [c !. Selective extraction of copper with organic solvent
    [0172] Selective extraction of copper from the rich solution of Cu and Zn (4) by means of the solvent extraction technique and using a specific organic extractant (RH1), to obtain a purified aqueous solution loaded with Cu (5) and a spent raffinate that contains Zn (6), according to the ion exchange reaction that takes place between the aqueous and organic phases:
    [0173] (vi) 2 RH1 (org) Cu2 + = R 2 Cu 2 H +
    [0175] Stage [d !. Copper electrodeposition
    [0177] Obtaining copper metal in the form of high purity copper cathodes (7) by electrodeposition from the purified and loaded solution of Cu (5), according to the reactions (g) and (h) that take place in the cathode and in the anode of the copper electrolysis cells respectively:
    [0178] (vii) CuSO4 2 e- = Cu0 SO 4 2- (viii) H 2 O - 2 e- =% O 2 + 2 H +
    [0179] Global reaction: CuSO 4 + H 2 O = Cu 0 +% O 2 + H 2 SO 4
    [0181] Stage Te !. Iron removal
    [0183] Elimination of the iron present in the spent refining (6) by chemical precipitation, previous oxidation of Fe (II) to Fe (III) with air or oxygen, adjusting the pH with an alkali such as calcium hydroxide, as shown in the reaction (i), obtaining a solution loaded with zinc and free of iron (8) and a solid residue with the iron salts precipitated together with the gypsum formed (9). A portion of the solid residue (10) is contacted with the zinc raffinate-1 (12) to re-leach iron (III) and recycle it to Step [a] as ferric sulfate, as shown in the reaction (x).
    [0184] (ix) Fe 2 (SO 4) 3 + 3 Ca (OH ) 2 + 4 H 2 O = 2 FeO (OH) 3 CaSO4.2H2O
    [0185] (x) 2 FeO (OH) 3 H 2 SO 4 = Fe 2 (SO 4) 3 + 4 H 2 O
    [0187] Stage rfl. Selective extraction of zinc with organic solvent
    [0189] Solvent extraction of zinc from solution ( 8 ) using a specific organic extractant for zinc (RH2), in order to obtain a purified aqueous phase loaded with Zn (11) and a raffinate-1 with a low content of it ( 12), which is recycled to Step [a]. The ion exchange reaction that occurs is the following between the aqueous phase and the organic phase:
    [0190] (xi) 2 RH2 (org) Zn2 + = R 2 Zn 2 H +
    [0192] Stage [g]. Electrodeposition of zinc
    [0194] Obtaining zinc metal in the form of high purity cathodes (13) by electrodeposition from the purified and charged aqueous solution of Zn (11), according to reactions (xii) and (xiii) that take place at the cathode and in the anode of the zinc electrolysis cells respectively:
    [0195] (xii) ZnSO4 2 e- = Zn0 SO 4 2- (xiii) H 2 O - 2 e- =% O 2 + 2 H +
    [0196] Global reaction: ZnSO 4 + H 2 O = Zn 0 +% O 2 + H 2 SO 4
    [0198] Stage [h]. Atmospheric leaching in chloride medium
    [0200] Second stage of atmospheric leaching of the leached solid residue (3) from Stage [b], which contains Pb and Ag sulfates, in a hot solution concentrated in chlorides, such as sodium chloride, adding sulfuric or hydrochloric acid to adjust the pH and obtain a leached pulp (14) that passes to the next stage. The main reactions that occur in this stage of atmospheric leaching of lead and silver are:
    [0201] (xiv) PbSO4 4 NaCl = Na 2 PbCU Na2SO4
    [0202] (xv) Ag2SO4 4 NaCl = 2 NaAgCh Na2SO4
    [0204] Stage [i]. Solid / liquid separation in the leached silver lead pulp
    [0206] Separation of the leached solid residue (15) and a solution rich in Pb and Ag (16) using conventional thickening and filtration equipment.
    [0207] NI stage. Silver recovery
    [0209] Recovery of silver from solution (16) by chemical reduction with a metal with an oxidation potential greater than silver (M1) such as lead (it is possible to use other metals, including iron, zinc or aluminum), depending on is shown in reactions (xvi) and (xvii), to obtain a product of metallic Ag: silver cement (17), and a solution enriched in Pb and free of Ag (18). A suitable portion of the silver cement is recycled to step [a] to act as a catalyst in the leaching of Cu and Zn.
    [0210] (xvi) M10 - x e- = M1x +
    [0211] (xvii) x Ag1 + - x e- = x Ag0
    [0212] Global reaction: M10 x Ag1 + = M1x + x Ag0
    [0214] Stages [k] and [l]. Lead recovery
    [0216] Recovery of lead from the solution enriched in Pb (18) by chemical reduction with a metal with an oxidation potential greater than lead (M2) such as iron, zinc or aluminum, to obtain a metallic lead product (20) in the form of fine particles, as shown in reactions (r) and (s), and a depleted solution in Pb (21) that is recycled to Step [h]; To avoid the accumulation of certain components in the main circuit, a small purge is carried out in this solution. The metallic lead product (20) passes to stage I where it is compacted to form briquettes, and then it is melted and strained, obtaining as a final product high purity lead ingots (22). A suitable portion of the lead produced is recycled to Stage j to act as a silver reducer. (r) M20 - and e- = M2x +
    [0217] (s) and Pb2 + - and e- = and Pb0
    [0218] Global reaction: M20 and Pb2 + = M2y + and Pb0
    [0220] Examples
    [0222] The present invention is further described by means of the following examples, which should not be considered limiting, in which the preferred embodiments are detailed.
    [0224] Example 1. Atmospheric leaching of polymetallic global concentrates in one stage by adding silver catalyst
    [0226] Several single-stage atmospheric leaching tests were performed on a scale of laboratory, using one-liter glass reactors equipped with a magnetic stirrer, on two samples of global polymetallic concentrates from different sources, which have been called Concentrate A and Concentrate B, in order to test the effect of the addition of silver as a catalyst . The composition of the concentrates and the operating conditions are shown in the following tables.
    [0228] Table 1. Composition of concentrates
    [0233] Table 2. Operating conditions in example 1
    [0238] Copper and zinc are present in the form of metal sulphides, chalcopyrite and blende respectively, in the treated global concentrate samples and are leached according to reactions (a) and (b) and go into solution. The leaching efficiency has been calculated as the percentage of each of these metals that have dissolved during the leaching process with respect to the content of said metals in the initial weight of feed concentrate; the copper and zinc extraction percentages are summarized below:
    [0240] Table 3. Copper and zinc extraction percentages in example 1
    [0243] It is observed that the addition of the silver catalyst notably increases the leaching of copper from chalcopyrite, but at the same time reduces the leached zinc, this effect being more negative in the case of Concentrate B, which goes from recovering 96.9% of zinc Without adding silver catalyst to recover 82.6% of zinc in the presence of silver.
    [0245] Example 2. Atmospheric leaching of polymetallic global concentrates in two stages by adding silver catalyst
    [0247] Since the addition of silver as a catalyst can decrease the extraction of zinc in the atmospheric leaching of polymetallic global concentrates, in this example the atmospheric leaching process was carried out in two stages of concentrate B, the first without adding silver, and the second by adding silver. The laboratory equipment used was the same as in the previous example, that is, glass reactors with a capacity of one liter fitted with a magnetic stirrer. The operating conditions are as follows:
    [0249] Table 4. Operating conditions for example 2
    [0254] Copper and zinc are present in the form of metal sulphides, chalcopyrite and blende respectively, in the treated global concentrate samples and are leached according to reactions (a) and (b) and go into solution. The leaching efficiency has been calculated as the percentage of each of these metals that have dissolved during the leaching process with respect to the content of said metals in the initial weight of feed concentrate; the copper and zinc extraction percentages are summarized below: Table 5. Copper and zinc extraction percentages from example 2
    [0259] It is observed that when atmospheric leaching is carried out in two stages, the first without adding silver, and the second adding silver as a catalyst, efficient leaching of both metals, copper and zinc, is achieved in the global concentrates checked.
    [0261] The previous results allow defining two different flow diagrams to achieve efficient atmospheric leaching of global polymetallic concentrates, depending on their behavior against the addition of silver as a catalyst. In Figure 1 atmospheric leaching is illustrated in a single stage, with the silver catalyst being added at the beginning of the leaching process; This diagram is applicable to polymetallic concentrates where both copper and zinc are efficiently leached thanks to the catalytic effect of added silver. Figure 2 illustrates the two-stage leaching, with the first stage of the atmospheric leaching process running without adding silver catalyst, while the second leaching stage takes place once said catalyst is added; This diagram is applicable to polymetallic concentrates where the silver catalyst produces a reduction in the zinc leaching efficiency, so that in the first stage a high zinc extraction is achieved without the presence of the silver catalyst, while in the second leaching stage, once said catalyst is added, it is possible to efficiently extract the copper from the chalcopyrite.
    [0263] Example 3. Atmospheric leaching of global polymetallic concentrates by adding chlorides together with the silver catalyst
    [0265] Several laboratory scale atmospheric leaching tests were carried out in a single stage, using the same equipment mentioned in the previous examples, one-liter glass reactors equipped with a magnetic stirrer, on two samples of polymetallic global concentrates A and B. In some tests only the silver catalyst was added, while in other tests the silver catalyst and sodium chloride were added together. The operating conditions are as follows: Table 6. Operating conditions of Example 3
    [0270] Copper and zinc are present in the form of metal sulphides, chalcopyrite and blende respectively, in the treated global concentrate samples and are leached according to reactions (a) and (b) and go into solution. The leaching efficiency has been calculated as the percentage of each of these metals that have dissolved during the leaching process with respect to the content of said metals in the initial weight of feed concentrate; the copper and zinc extraction percentages are summarized below:
    [0272] Table 7. Copper and zinc extraction percentages from example 3
    [0277] It is observed that the addition of the silver catalyst together with sodium chloride notably increases the leaching of zinc, this effect being more notable in the case of Concentrate B, which goes from recovering 82.6% of zinc by adding only the silver catalyst to recover 95.5% of zinc when the silver catalyst is added together with sodium chloride.
    [0278] The previous results show that it is possible to define two process options to achieve a high recovery of zinc from global polymetallic concentrates, one of them consists of carrying out atmospheric leaching in two stages, as described in Figure 2, and the other possibility is to apply atmospheric leaching in one stage, as described in Figure 1, adding together the silver catalyst and the chloride of sodium.
    [0280] Example 4. Atmospheric leaching of global polymetallic concentrates by adding recycled silver cement as silver catalyst
    [0282] Several laboratory scale atmospheric leaching tests were carried out in a single stage, using glass reactors of three liters of capacity equipped with stirrers with variable speed, on a sample of polymetallic global concentrate, which has been called Concentrate C, in order to test the effect of adding silver in the form of recycled silver cement versus a silver sulfate salt. The composition of the concentrate and the operating conditions are shown in the following tables.
    [0284] Table 8. Composition of the concentrate of example 4
    [0289] Table 9. Operating conditions of Example 4
    [0294] The main components of recycled silver cement are metallic lead (90%) and metallic silver (5%).
    [0296] Copper and zinc are present in the form of metal sulphides, chalcopyrite and blende respectively, in the concentrate and are leached according to reactions (a) and (b) and go into solution. The leaching efficiency has been calculated as the percentage of each of these metals that have dissolved during the leaching process with respect to the content of said metals in the initial weight of feed concentrate; the percentages of copper and zinc extraction in concentrate C are summarized below:
    [0297] Table 10. Copper and zinc extraction percentages from example 4
    [0302] It is observed that the addition of silver as a catalyst, either as a silver sulfate salt or as a recycled silver cement, substantially increases the leaching of copper and zinc in this overall concentrate compared to the case of without the addition of silver catalyst. It can also be observed that the addition of recycled silver cement has a catalytic effect very similar to that of the silver sulfate salt, even with a much lower dose: 150 g / t of solid versus 700 g / t of solid of the salt of silver. Possibly, silver cement has a higher catalytic activity than silver salt because it is made up of nano-crystalline-sized metal particles and a large specific surface area.
    权利要求:
    Claims (12)
    [1]
    1.- Procedure for the extraction of metals from minerals or polymetallic concentrates, which comprise Cu sulphides in the form of chalcopyrite, and Zn, Pb and Ag sulphides, which comprises the steps of:
    a) A first stage of leaching at atmospheric pressure, in a sulfate medium, of the initial raw material (1): minerals that comprise Cu sulfides in the form of chalcopyrite, and Zn, Pb and Ag sulfides or polymetallic concentrates that comprise sulfides of Cu in the form of chalcopyrite, and sulfides of Zn, Pb and Ag, in the presence of oxygen and ferric sulfate, with the addition of sulfuric acid and a silver catalyst to obtain a solution rich in Cu and Zn (4) and a solid leachate containing Pb and Ag (2) as sulfates;
    b) separation of the solution rich in Cu and Zn (4) and the leached solid containing Pb and Ag (2) from step a) above, in the form of a leached residue of precipitated Ag and Pb sulfates; c) extraction of Cu by adding a specific organic extractant for copper to the solution rich in Cu and Zn, to obtain a purified and loaded solution of Cu (5) and an exhausted raffinate containing Zn (6);
    d) obtaining Cu (7) by electrodeposition from the purified and loaded solution of Cu (5) obtained in step c);
    e) elimination of the Fe present in the spent raffinate from step c) above by precipitation through the oxidation of Fe (II) to Fe (III) and pH adjustment between 3 and 4, obtaining a solution loaded with Zn and free of iron and an iron precipitate; part of the iron precipitate is recycled to stage a) to provide and maintain the necessary concentration of Fe (III);
    f) Purification and concentration of the solution loaded with Zn (8) and free of iron from step e) by adding an organic extractant specific for zinc to the solution loaded with Zn (12), to obtain a purified solution and loaded with Zn (11) and a raffinate containing residual zinc (12) that is recycled to step a) above;
    g) obtaining Zn (13) by electrodeposition from the purified and charged solution of Zn (11);
    h) second stage of atmospheric leaching of the leached residue (2) comprising Pb and Ag from stage b) in a solution in saturated water of a chlorine salt at a temperature between 60 ° C and 100 ° C, giving rise to a charged solution of Ag and Pb (16);
    j) recovery of Ag, from the solution loaded with Ag and Pb (16) by reducing it with lead metal, recycling of the next stage k), to form an Ag cement (17) and a solution enriched in Pb (18); part of the silver cement produced is recycled as a catalyst to stage a);
    k) recovery of Pb from the Pb-enriched solution by chemical reduction adding metallic aluminum, to form a lead cement and a spent solution that is recycled to step h) of this process; a part of the lead produced is recycled to stage j) to cement the silver.
    [2]
    2. - Metal extraction process according to claim 1, characterized in that stage a) is carried out in two successive sub-stages, the first sub-stage without adding the silver catalyst and the second sub-stage adding the silver catalyst , maintaining the rest of the conditions according to claim 1.
    [3]
    3. - Metal extraction process according to any one of claims 1 to 2, characterized in that in step a) chloride ions are added in the form of salt until reaching a concentration greater than 0.4 g / l of chloride ions in the leaching solution.
    [4]
    4. - Process according to any one of claims 1-3 characterized in that in step a) the leaching time is in a range between six hours and twenty-four hours, and the temperature is between 80 ° C and 100 ° C.
    [5]
    5. - Process according to any one of claims 1-4 characterized in that in step a) the added sulfuric acid is in a range between 20g / l and 100g / l.
    [6]
    6. - Process according to any one of claims 1-5 characterized in that in step a) the iron concentration is in a range between 5g / l and 50g / l.
    [7]
    7. - Process according to any one of claims 1-6 characterized in that in step e) of iron removal, milk of lime or limestone or zinc oxides are added, and air, enriched air or oxygen is injected.
    [8]
    8. - Process according to any one of claims 1-7 characterized in that in step h) the leaching time is in a range between one hour and three hours, and the temperature is between 60 ° C and 100 ° C.
    [9]
    9. - Process according to any one of claims 1-8 characterized in that in step h) the pH is in a range between 0.2 and 4.0.
    [10]
    10. - Process according to any one of claims 1-9 characterized in that in step h) the concentration of chloride ions is in a range between 1.5N and 4.5N.
    [11]
    11. Process according to any one of claims 1-10, characterized in that in step j) other metals with an electrode potential lower than silver can be added.
    [12]
    12. Process according to any one of claims 1-11 characterized in that in step h) other metals with a lower electrode potential than lead can be added.
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    同族专利:
    公开号 | 公开日
    AU2020203164A1|2020-12-03|
    CA3081014A1|2020-11-17|
    ES2794298B2|2021-05-31|
    EP3739069A1|2020-11-18|
    AU2020203164B2|2021-03-04|
    EP3739069B1|2022-01-05|
    US20200362435A1|2020-11-19|
    PE20201058A1|2020-10-15|
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