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    • 专利摘要:
    Hydrometallurgical plant for the treatment of complex sulfides. It is a hydrometallurgical plant for the treatment of complex sulfides, specifically, a process for the extraction of copper and zinc from said sulphides by leaching at atmospheric pressure in aqueous medium and operating at a temperature below 100ºC. The procedure described allows the direct treatment of the ore (All One), with low grades in copper and zinc, as well as the treatment of global flotation concentrates. The leaching is carried out in one stage, using ferric sulphate as the oxidizing agent of the sulfides that is generated in an oxidation-precipitation stage of the solution coming from the leaching of the sulfides. To favor the oxidation with atmospheric air of the ferrous ions generated during the leaching of copper and zinc, the solution is neutralized up to pH 4.5-5.0 with ammonia. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2674440A1
    申请号:ES201601106
    申请日:2016-12-29
    公开日:2018-06-29
    发明作者:Santiago DEL BARRIO MARTÍN；Antonio GUIJARRO FRANCO；Victor CONTRERAS GONZÁLEZ DEL POZO
    申请人:Inst Geologico Y Minero De Espana Museo Geominero；Instituto Geologico Y Minero De Espanamuseo Geominero；Proton Ingenieros Slp；
    IPC主号:
    专利说明:

    OBJECT OF THE INVENTION
    The present invention relates to a hydrometallurgical process for the treatment of
    10 complex sulphides, the procedure based on an initial direct leaching of copper and zinc sulphide, using ferric sulfate as a sulfuric medium and operating at temperatures below 100 ° C. 15 BACKGROUND OF THE INVENTION
    Direct leaching of metal sulfide ores is a chemical dissolution process whereby, in the presence of a suitable oxidizing agent, metal sulphides dissolve in mineral acids to provide a solution of metal salts and sulfur
    20 elementary; the kinetics of the reaction between the different sulfides and the selected leaching agent or agents being the determining factor of the process.
    Most known hydrometallurgical processes take place in sulfate medium. Ferric sulfate in acidic medium has a wide field of application as an agent
    Leaching using the easy reduction of ferric salt to cause the oxidation of other compounds but, to achieve a high yield, it is necessary to have a high Fe3 + concentration. The attack of the ferric ion to the metal sulphides takes place from a mechanism of electrochemical nature, the kinetics of these reactions being strongly influenced by temperature. The main reaction that takes place is as follows:
    where I can be Zn, Cu, Pb, Ag, etc.
    35 During this reaction Fe3 + is transformed into Fe2 +, it being necessary to reoxidate this Fe2 +
    in order to maintain a high concentration of Fe3 +. This oxidant can be the oxygen in the air, according to the following reaction:
    The oxidation of the ferrous form, Fe2 +, presents serious economic difficulties because the cheap agent that caused it has not been found. After discarding for economic reasons the oxidation by classic agents such as permanganate, hydrogen peroxide, oxygen of high purity, etc., remains the only agent of interest the oxygen in the air.
    Ferric ion (Fe3 +) in an acidic medium is widely applied in the mineral products industry as an oxidative leaching medium for the material that needs to be oxidized to make it soluble. This is always one of the earliest stages in a hydrometallurgical extraction procedure since once the metals have been solubilized, their separation and purification can be performed according to a large number of established hydrometallurgical unit operations.
    Although it has been found that the ferric ion is a convenient and very effective oxidizing agent in an acidic aqueous medium, the final potential gradient for oxidation (i.e., final electron acceptance in scientific terms) is normally provided by oxygen, both in the form of atmospheric air or as a purer form of oxygen. This is due to the fact that oxygen would be supplied to the process to oxidize soluble iron from a low oxidation state (ferrous ions, Fe2 +) to a high oxidation state (ferric ions, Fe3 +). The ferric ion, being also an acceptor of electrons, each in turn carries the oxidative power to the mineral where it reacts with the mineral according to mechanisms that are more complex than the stoichiometric equations reveal. The oxidized mineral dissolves and the iron returns to the ferrous state, which can be oxidized again with ammonia and air and thus the cycle continues. For physical and chemical reasons, the direct reaction between gaseous oxygen and solid mineral surfaces in complete absence of soluble iron is economically less feasible.
    However, special conditions are required to achieve the reaction between soluble iron and oxygen at an effective cost. One possible approach is to use a high temperature, typically above the normal boiling point of water, in a
    Pressurized reaction vessel to achieve an acceptable reaction rate and the extent of oxygen utilization in the reaction between oxygen and soluble iron.
    Many minerals can oxidize to various degrees, depending on the conditions chosen. For example, complex sulfides consist of metal atoms attached to sulfur atoms. Depending on the conditions, the associated sulfur atom could be oxidized from its sulfide form, to elemental sulfur or to dissolved sulfate ions, which will depend on the amount of oxygen required and the temperature. In both cases, the metal ions will be solubilized, which is the ultimate objective of oxidation.
    If the leaching of the mineral and the oxidation of the iron occur in separate vessels has advantages, because the conditions for the two reactions can be optimized independently and the conditions for the leaching of the mineral could be chosen such as to favor a greater range of elemental sulfur, contrary to sulfate, formation that would have been the case under the conditions chosen for the oxidation of iron.
    Ferric iron regeneration takes place at an independent stage of leaching, using air to carry out oxidation and maintaining the pH value at 4.5. This is a great advantage from an economic point of view compared to other processes that use pure oxygen for oxidation.
    The solution obtained in the neutralization-oxidation process, with a total iron concentration <1 ppm, is incorporated into the stage of extraction of Cu and Zn by solvents for its subsequent purification and recovery of copper and zinc by electrolysis.
    The recovery of the leaching agent (Fe (III)) is carried out for 2 purposes. The first, for subsequent recirculation and, the second, to avoid interference in the solvent extraction stage for the recovery of Zn and subsequent electrolysis, since Fe (lIl) corrodes the cathodes.
    The extractants used for the zinc extraction stage extract iron (both ferrous and ferric) at the same time as zinc, although in each recirculation the solvent loses the ability to extract zinc until it is completely inactive for its extraction. In the re-extraction stage, said iron is re-extracted, passing to the electrolyte, which generates the difficulties that have been observed in electrolysis. Therefore it is necessary to remove iron from liquor before solvent extraction and electrolysis. This step may be incorporated before solvent extraction of Cu or after solvent extraction of Cu and prior to that of Zn.
    A series of patents related to complex sulfide leaching procedures are cited below:
    Patent 414173 for: "High temperature pressure leaching process in aqueous medium of complex sulphides".
    This document refers to the hydrometallurgical treatment of complex sulfides of iron and other non-ferrous metals, and more specifically, the process of extracting copper and zinc from said sulfides by pressure oxidation (5.0 -18 Kg / cm2 g) in aqueous medium and 15 high temperature (> 175 ° C <220 ° C). The gas used preferably is oxygen, although air and oxygen enriched air can also be used. The described method allows the direct treatment of minerals with a low concentration of copper and zinc, although it is preferably applied to global flotation concentrates. The procedure can be used to process copper and zinc concentrates formed by different species
    20 mineralogics such as chalcopyrite, covelite, bornite, chalcocite, blenda esfarelita, etc.
    Patent 2 137 871 for "Hydrometallurgical process for the benefit of poly metallic pyrite minerals".
    25 This document refers to a hydrometallurgical process for the benefit of pyritic minerals, which deals with the treatment of polymetallic sulphides of iron and other non-ferrous metals, and specifically of pyrite-based minerals containing smaller amounts of copper, zinc sulphides , lead and silver, such as those known as complex pyrites abundant in the Pyritic Belt of the SO of the Iberian Peninsula, and more
    30 specifically to the extraction of copper and zinc, lead and silver from said sulphides by means of a hydrometallurgical process that combines oxidation operations in aqueous medium with oxygen at pressure and high temperature, with extraction operations with selective copper and zinc solvents, with operations Cementation of lead and silver solubilized in the leaching of solid waste with brine, and with membrane separation operations for minimization and recycling of brine and wastewater.
    Patent: ES 2 064 285 for: "Copper sulfide bioleaching process by indirect contact with effect separation".
    It consists of a bioleaching process of copper sulphide ores and their flotation concentrates, characterized by the use of indirect contact bioleaching with separation and potentiation of chemical and biological effects. For the chemical stage, low concentration ferric sulfate is used as a leaching agent. For the biological stage, whose objective is the oxidation and regeneration of the leaching liquor to transform the ferrous ion to ferric and recycle said liquor to the leaching reactor, bacterial films of Thiobacilus ferrooxidans supported in inert solid are used. The process allows the total extraction of the copper contained in the ore, obtaining a leaching liquor with the entire copper charge and a concentration of ferric sulfate as low as the one initially used, so that it can be treated without difficulty by solvent extraction and electrolysis to obtain cathode copper.
    Patent: 2294958 for "Oxidative leaching procedure".
    The invention provides a process for the oxidative leaching of a metal or a metal component of a material containing the metal or a metal component that includes at least one step of acid production and at least one step of acid consumption in which the acid in the acid production phase is partially available to the acid consumption phase. The process may also include the use of an intermediate agent to transfer the oxidative capacity to the material to be leached, said intermediate agent preferably comprises iron or chloride.
    Patent: ES 2 017 554 for "Procedure for integral use of complex sulphides".
    According to this procedure for the integral use of sulphide minerals, the mineral conditioned to adequate particle size is subjected to a wet treatment, with an oxidizing agent originating two streams, a liquid containing dissolved non-ferrous and precious metals in such a way that they can be recovered by regenerating at the same time the leaching solution that is susceptible to recirculation and another solid that is subjected, in a closed circuit in an inert atmosphere and with indirect heat input to a distillation in a fluid bed at a moderate temperature to distill the sulfur together with the other volatile elements leaving a residue that is subjected to a third stage to an acid leaching in which gaseous hydrogen sulphide is produced, partially usable in the Claus process itself, and a bleach containing the pyrrhotic iron in the form of ferrous salt and is susceptible , once purified, to regenerate the leaching agent and produce iron oxide of high quality.
    Patent: 2 192 133 for "Procedure for leaching zinc sulphide concentrates".
    It consists of a method for leaching zinc sulphide concentrates at atmospheric pressure, in an open tank, integrated in a conventional hydrometallurgical process (roasting-leaching-electrolysis). The leaching of the zinc concentrate is carried out in two stages in countercurrent, using as a sulfur oxidizer a precipitate of ferric hydroxide that is generated in a neutralization-oxidation stage of the solution from the leaching of the zinc sulphide concentrate. To favor the oxidation with atmospheric air of the ferrous ions generated in the extraction of zinc, the solution is neutralized to pH 4.5-5.0 with calcine from roasting. Under these conditions iron (111) precipitates in the form of hydroxide. DESCRIPTION OF THE INVENTION
    The present invention relates to a hydrometallurgical process for the treatment of complex sulfides of copper and zinc. The leaching of copper and zinc sulphides is carried out at atmospheric pressure, in open reactors, at a temperature between 80 and 100 ° C.
    For a hydrometallurgical process to be complete for the extraction and recovery of metals from complex sulfides, at least the following stages are required:
    1. Mineral leaching stage (that is, in which the ore comes into contact with ferric iron).
    2. Ferrous iron chemical oxidation stage
    5 3. Metal extraction stage, in which the valuable metal is obtained from dissolution in a salable form.
    In the case of metals such as copper and zinc, metal is commonly produced in the form of metal cathodes, by the application of electrical energy (electrolytic extraction),
    10 which is also typically preceded by a solvent extraction step, for purposes such as obtaining a solution in which the valuable metal is in a purer and more concentrated form than what is in the leaching solution that arises from of the mineral leaching stage.
    15 In each of the process steps mentioned above, interrelated chemical reactions take place that involve, apart from the valuable component and other species, also acid and iron. The established hydrometallurgical practice for purging iron from a procedure is to add an acid neutralizing agent, such as lime and / or limestone, to a solution containing iron in a ferric form that causes the
    Iron precipitates in solid form, so it could be separated from the liquid phase, typically by sedimentation and / or filtration. Specifically, the iron form of iron is favored by that stage, since ferric iron is much less soluble and therefore precipitates much faster than ferrous iron. The ferric precipitate is also less likely to be redissolved after disposal than the iron precipitate would.
    25 ferrous. In this invention the neutralizing agent is ammonia maintaining the pH and at the same time aerating to favor the oxidation of ferrous to ferric in less time.
    Another important aspect of the leaching of complex sulphides revolves around the control of the redox potential, so we could selectively leach only 30 components of a mixture of minerals, controlling this within the limits within which certain components of the mixture are they would leach and others not.
    Unlike existing processes, ferric ion regeneration takes place at a stage independent of leaching, using atmospheric air to provide oxygen
    necessary to carry out the oxidation and maintaining the pH at 4.0-5.5.
    In these conditions the ferric ion precipitates in the form of hydroxide. This is an advantage from the economic point of view compared to other processes that use pure oxygen of high purity. Different bases can be used as neutralizing agent. Among them, ammonia has a number of advantages as it can be added to the solution in a continuous and controlled manner, it is a cheap and affordable product and does not interfere with the quality of the precipitate obtained. DESCRIPTION OF THE DRAWINGS
    To complement the description that will then be made and in order to help a better understanding of the characteristics of the invention, according to a preferred example of practical implementation thereof, a set of drawings is attached as an integral part of said description. where, for illustrative and non-limiting purposes, the following has been represented:
    Figure 1 shows a flow block diagram of the process of direct oxidation of complex sulfides.
    Figure 2.- Shows a diagram of the redox potential as a function of pH, or Pourbaix diagram. PREFERRED EMBODIMENT OF THE INVENTION
    According to the aforementioned figures, the hydrometallurgical process of the invention is characterized by comprising the following phases:
    A stage A of leaching of the mineral, in which the mineral is fed (1) and contacted with ferric iron.
    The leaching of zinc and copper sulphides takes place according to the following reactions: The rest of the sulphides of other metals such as iron, lead or silver are also leached by the action of ferric iron, and reactions similar to the previous one can be written.
    The oxidation process must be carried out under conditions in which the pyrite does not oxidize considerably. The maximum operational dissolution potential, that is, the potential at which the process is carried out, must be less than 500mV and greater than 380mV to facilitate leaching of chalcopyrite.
    The leaching is carried out in a single stage in open reactors provided with mechanical agitation where the sulfides are leached with the Liquor O from the redisolution of the hydroxide corresponding to the block (6). Leaching takes place at atmospheric pressure and at a temperature above 900 C, for 3-4 hours.
    Once the ferric has been depleted and transformed into ferrous, the pulp is sent to a solid-liquid separation stage (2), where the solid corresponds to the residue (5). The clear clear phase of solids depleted in ferric ion and charged in ferrous ion is sent the stage
    (3) Solvent copper extraction for subsequent electrodeposition (4).
    In Stage B the extraction -re-extraction of leached Cu (Liquor A) is performed, according to the blocks or stages (3 and 3 ') and subsequent electrodeposition and, in which the following reactions occur:
    The liquor B leaving the copper extraction stage (3) (aqueous phase) passes to a stage
    (7) Oxidation neutralization and subsequent redisolution, according to stage C of the process, after which a liquid / solid separation process is carried out (13).
    The organic phase loaded with Cu is re-extracted with sulfuric acid and to recover it is carried
    to electrolytic cells.Below are the reactions involved in the electrolysis of copper togetherwith the compositions of its cathode and anode:
    Cathode (stainless steel): Cu 2+ + 2e - + Cu (s) Anode (Pb 98% + Sn 1.35%): H20 - + ~ 0 2 + 2H + + 2e-
    A high purity Cu (8) cathode and the Cu free liquor from the stage is obtained
    (4) of electrodeposition, is recirculated to Stage O as a source of acid, this stage corresponding to block (6).
    Stage C chemical oxidation of ferrous iron. .
    The oxidation of iron (11) by the oxygen of the air is possible thanks to the constant displacement of the equilibrium towards the ferric form due to the precipitation of the hydroxide, with the consequent reduction of the redox potential.
    When the oxygen in the air comes into contact with the ferrous ion, it oxidizes by giving an electron to the oxygen to become a ferric ion:
    The ferric ion liquor O has a great affinity for the hydroxyl ions of the water, therefore, it takes them, to form the ferric hydroxide through the following reactions:
    FeOH2 ++ H20 -.Fe (OH) 2 + + H + FeOH2 ++ H20 -. Fe (OH) J + H +
    The precipitate obtained, ferric hydroxide, is filtered off and used as Fe3 + in the leaching stage, according to the following reaction:
    2Fe (OHh (s) + 3H2S04 (ac) - Fe2 (S04) J (ac) + 6H20 (1)
    Liquor A from stage A has a minimum of 5 gIl of Fe3 + and 20-30 gIl of Fe2 + and a pH = 1 with H2S04. This solution, after solvent extraction from Cu, is neutralized with ammonia at pH 4.0-5.5. This stage is carried out in an agitator tank introducing the ammonia necessary to maintain in said reactor pH 5. In this stage the oxidation, with finely dispersed air, of the ferrous to ferric ion, and the simultaneous precipitation of the hydroxide of ferric Oxidation is very favorable under these conditions, since the redox potential of the Fe3 + / Fe2 + system, which is 0.77 V in an acid medium, decreases rapidly when the pH is reached by stabilizing Fe3 + in the form of hydroxide, reaching a pr value. or at 0.3 V for pH 5. Under these conditions it is possible to carry out oxidation with atmospheric air without using oxygen or enriched air. In order to achieve a high rate of formation of ferric precipitates, the oxidation phase (process control stage) is favored by increasing the ferrous air-liquor contact by distributing air in the suspension by means of a turbo stirrer at a high rotational speed.
    In order to achieve a high rate of formation of ferric precipitates, the oxidation phase (process control stage) is favored by increasing the ferrous air-liquor contact by distributing air in the suspension by means of a turbo stirrer at a high rotational speed.
    In aqueous solutions, the pH changes cause significant variations in the redox potential of the system, which is verified by the Nerst equation, such changes in pH and redox potential can cause variations in the results of the redox processes that develop, causing The formation of different species. The most convenient way to represent the thermodynamics of aqueous systems is graphically in Pourbaix diagrams or potential -pH diagrams.
    These diagrams are widely used by hydrometallurgists, because they allow visualizing possibilities of reactions without having to resort to thermodynamic calculation for phenomena that occur in aqueous media.
    The graphical representation of the redox potential as a function of pH (Pourbaix diagram) in Figure 2 shows the main thermodynamically stable species for the Fe3 + / Fe2 + system.
    The oxidation by oxygen of the air is possible thanks to the constant displacement of the equilibrium towards the ferric form due to the precipitation of the hydroxide, with the consequent reduction of the redox potential. The ferric hydroxide precipitate is separated by decantation-filtration. The solution obtained in the neutralization-oxidation process, with a total iron concentration <1 ppm, is incorporated into a stage of Zn extraction by solvents Stage E corresponding to block (8), for its subsequent purification and recovery of zinc by electrolysis, while the precipitate passes to Stage D.
    The precipitate contains lead, silver and gold that can be subject to further treatment for recovery if it is economically profitable.
    In step D, corresponding to block (6), the precipitate of ferric hydroxide is redissolved with sulfuric acid between 7.5% -10% obtaining a liquor with 25g / l-30 gIl of Fe3 + that is recycled, for the most part, to stage A as a leaching agent.
    If it is necessary to purge part of the iron solution obtained, the solution can be precipitated as a jarosite or any other easily precipitated iron precipitate.
    Stage E of extraction -re-extraction by solvents of Zn and subsequent electrodeposition, corresponding to the blocks (8, 9 and 10).
    In this stage the extraction -re-extraction of the Zn of the Liquor e is carried out, coming from the stage of the Stage e and subsequent electrodeposition and, in which the following reactions occur:
    (Zn2 + + S042-) aq + (2RH) org -> (R2Zn) org + (2H + + S042-) aq (R2Zn) org + (2H + + S042-) aq -> (2RH) org + (Zn2 + + S042- ) here
    The organic phase charged with Zn which is re-extracted with sulfuric acid and to recover it is taken to the electrolytic cells.
    The reactions involved in the electrolysis of zinc together with the compositions of its cathode and anode are indicated below:
    Cathode (99.8% at 1050): Zn2 + + 2e -> Zn (s)
    A high purity Zn cathode (11) is obtained and the resulting liquor E is recirculated to the redisolution stage E. (6) as the acid source.
    Therefore, and according to the aforementioned figure 1, in the flow chart of the complete hydrometallurgical process for the extraction and recovery of metals from complex sulphides it is necessary to separate the neutralization-oxidation stage C from iron (7 ) and the leaching stage A facilitate the optimization separately of the two procedures.
    Specifically, the leaching stage A requires previously determining the total ferric ion consumption necessary, depending on the ore laws and the stoichiometry of the reactions, for leaching. There is a limitation, if the sample needed 45g / l of Fe (lI) and was completely leached, the amount of Fe (lI) in solution would be 45g / l and it precipitates in concentrations greater than 40g / l. The influence of the solid / liquid ratio (SIL) is studied without varying the concentration of leaching agent Fe (llI) that is set at 30g / l.
    The Fe (llI) ion comes from the neutralization-oxidation stage (Stage C) and subsequent redisolution with sulfuric acid (Stage D) according to:
    The predetermined solids density of the poly metallic sulfide in relation to the liquor from Stage O is between 6.7 and 20%, the pH = 1 and the temperature> 90 - <100 ° C.
    5 The polymetallic sulphides that have been studied have as main mineralogical species to consider in leaching the following:
    The first three are those in which the best possible performance should be achieved, the last one is inevitable to occur to a certain extent.
    Leaching takes place in an open reactor with stirring, at atmospheric pressure during
    20 3h at all times controlling the pH = 1, the redox potential that does not fall below 380mV to facilitate leaching of the chalcopyrite by aerating and the temperature> 90 - <100 ° C.
    The leaching pulp is sent to the liquid solid separation stage (2) to a thickener and subsequent filtration, the liquid phase (Liquor A) being sent as liquor loaded with copper and zinc 25 to Stage B, extraction-re-extraction and electrodeposition of Cu.
    In stage B of solvent extraction-re-extraction according to blocks (3 and 3 ') and electrodeposition of Cu, according to block (4), the liquor of Stage A, at pH 1 loaded with Cu, Zn and Fe between others and at room temperature, a conventional installation of
    30 extraction with copper solvents using selective chelating agents of the next type, in this case it MAKES commercial M5460 which has a Cu / Fe selectivity of not less than 3000, so at this stage the presence of iron in any of its dissolving forms
    In this stage the stirring is controlled, time to establish the balance between the two phases, settling time, ambient temperature and atmospheric pressure. The aqueous phase from which copper (3) has been extracted by exchange with protons of the organic phase (ACORGA) is the sulfate-loaded zinc liquor that is sent to STAGE C. the copper extracted by the organic phase It is transferred to a copper sulphate electrolyte by re-extraction (3 ') with sulfuric acid for subsequent electrodeposition (4) with insoluble anodes in which copper cathodes (8) of high purity are obtained.
    Copper-free Liquor B 'is recirculated to Stage O as acidity supply for the redisolution of the ferric precipitate, according to block (6).
    Studying all the variables for this case you get that:
    • Copper solvent extraction has been carried out with Acorga M-5640 with 10% organic / kerosene ratios and 1: 1 O / A, with a recovery of 84.66% and,
    • The optimal re-extraction of copper, for these conditions, is with acidic water with 170000mg / 1 of H2S04 and O / A 1: 1, with a recovery of 92.88%.
    Subsequently, stage C, of chemical oxidation of Fe (II), is carried out.
    It has been commented that the recovery of the leaching agent (Fe (III)) is carried out with 2 purposes. The first, for subsequent recirculation and, the second, to avoid interference in the solvent extraction stage for the recovery of Zn and subsequent electrolysis, since Fe (llI) corrodes the cathodes. The extractants used for the zinc extraction stage extract iron (both ferrous and ferric) at the same time as zinc, although in each recirculation the solvent loses the ability to extract zinc until it is completely inactive for its extraction. In the re-extraction stage, said iron is re-extracted, passing to the electrolyte, which generates the difficulties that have been observed in electrolysis.
    Therefore it is necessary to remove iron from liquor before solvent extraction and electrolysis. This step may be incorporated before solvent extraction of Cu or after solvent extraction of Cu and prior to that of Zn.
    Liquor B is taken in a tank with stirring and aeration and the pH is raised with NH3 to 4.5-5, where Fe (lI) is in an aqueous form and subsequently aerated to oxidize Fe (lI) to Fe (III), that at that pH we ensure that it precipitates. The pH is maintained by adding NH3 and aeration is continued until the iron is around Oppm and the pH remains constant without changing.
    This pulp is filtered and the solid that will be redissolved with sulfuric acid (Stage O) is recovered and used as a leaching agent, making the process cheaper, while the liquor (Liquor C), where the metals of interest are located, will be taken to the stage Extraction with zinc solvents (Stage E).
    With neutralization -oxidation is achieved, after filtering:
    • a Liquor C loaded with Zn that is pumped to Stage E with Oppm of iron, in which 150L of ammonia is consumed per m3 of liquor B from the extraction of copper, which is subsequently pumped to Stage E for its extraction, Y
    • a Fe (lIl) precipitate of 80kg / m3 of liquor and its mineralogical composition is mostly Goetita and Lepidogrocita, both species susceptible to redisolution with sulfuric acid.
    In stage O, the redissolution of the Fe 111 ion precipitate is carried out for recovery of the leaching agent and recirculation to stage A, the Fe (lll) precipitate being redissolved with sulfuric acid and increasing the temperature to recirculate it as a leaching agent to Stage A.
    The most favorable conditions for this case are:
    • SIL ratio: 2.5%
    • Acid medium with H2S04: 10% • P:> 90 ° C
    • 90% redisolution
    This liquor O (regenerated ferric ion) is pumped to stage A as a leaching agent.
    In stage E the extraction (8), re-extraction (9) by solvents and electrodeposition (10) to zinc are carried out, so that the liquor of stage C, loaded with Zn and at room temperature, is pumped conventional installation of zinc solvent extraction using selective chelating agents of the carboxylic or phosphoric acid type as an organic phase, in this case CYANEX 302 (bis (2,4,4-trimethylpentyl) monothiophosphinic acid).
    In this stage the stirring is controlled, time to establish the balance between the two phases, settling time, ambient temperature and atmospheric pressure. In the aqueous phase, zinc has been extracted by cationic exchange of the organic phase (CYANEX).
    The zinc extracted by the organic phase is transferred to a zinc sulfate electrolyte by re-extraction with sulfuric acid for subsequent electrodeposition with insoluble anodes in which zinc cathodes (11) of high purity are obtained.
    Zinc-free Liquor E is recirculated to Stage O as an acid supply for the redisolution of the ferric precipitate.
    Studying all the variables for this case you get that:
    • zinc solvent extraction was carried out with Cyanex 302 with 5% organic / kerosene ratios and 1: 3 O / A, with a recovery of 99.72%. Y,
    • The optimal zinc extraction, for these conditions, is acidic water with 160000mg / l H2S04 and O / A 1: 2, with a recovery of 98.28%.
    权利要求:
    Claims (3)
    [1]
    1a ._ Hydrometallurgical plant for the treatment of complex sulphides, where copper and zinc sulphides are used in combination with ferric sulfate in sulfuric medium and operating at temperatures below 100oe, characterized in that an initial stage A of leaching prior to putting into contact of the mineral (copper and zinc sulphides) with ferric iron, after whose leaching stage solid products are obtained as waste and liquid products that correspond to a liquor A that are processed in a second stage S, where copper extraction takes place by solvents, the re-extraction of copper by solvents and the electro-deposition of copper, with the special feature that the liquor obtained in stage S is passed to a stage e of neutralization / oxidation of copper, obtaining liquid products and solids, where solids are taken to a redisolution stage D, which is also accessed by liquor S from the electrodep stage copper ossification, while the liquid product obtained in the neutralization / oxidation stage e, is a liquor e, which is processed in a stage E where zinc extraction takes place (8), zinc re-extraction (9) by solvents and electrodeposition of zinc (10), with the particular feature that in the redisolution stage D, a liquor D is obtained which is applied again to the stage A of leaching of zinc and copper sulphides, while the liquor E obtained in the electrodeposition stage of zinc is applied to the redisolution block (6) of stage D, as is the liquor S 'obtained in the electrodeposition of copper.
    2a ._ Hydrometallurgical plant for the treatment of complex sulphides, according to claim 1a, characterized in that the leaching stage A is carried out in a single stage, in open reactors and provided with mechanical agitation, where the sulphors are leached with the liquor D from the redisolution of the hydroxide of stage D, leaching taking place at atmospheric pressure and at a temperature exceeding 900e for a period of three to four hours.
    3a._ Hydrometallurgical plant for treatment of complex sulphides, according to claim 1, characterized in that in stage A, after the separation of the liquid and solid
    (2) the pulp is sent once the ferric has been exhausted and transformed into ferrous, the liquid phase corresponding to liquor A is sent to stage S where copper extraction by solvents takes place (3), as well as the re-extraction of the solvent copper (3 ') for later
    electrodeposition (4).
    Hydrometallurgical treatment for complex sulphides according to claim 1, characterized in that the copper and zinc metals obtained are obtained in the form of metal cathodes (8) and (11) respectively.
    Hydrometallurgical treatment for complex sulfides, according to claim 1, characterized in that in leaching a control of the Redox potential is established to effectively leach certain components of a mixture
    10 of minerals, in order to control the limits within which certain components of the mixture will be leached and others not.
    [0]
    0.6
    [-0]
    - 0.2 -0.6
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    同族专利:
    公开号 | 公开日
    ES2674440B2|2018-10-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US6746512B1|1998-08-24|2004-06-08|Technological Resources Pty. Ltd.|Hydrometallurgical extraction of copper and other valuable metals|
    CN102787237A|2011-05-20|2012-11-21|中国科学院广州地球化学研究所|Process for recovering iron, copper, zinc, and lead in copper tailing by leaching|
    CN103882236A|2012-12-19|2014-06-25|沈阳有色金属研究院|Method for processing high-sulfur copper dust and recovering copper by employing a wet process|
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