WO2012081953A1 - Means for the leaching of copper from refractory minerals - Google Patents

Means for the leaching of copper from refractory minerals Download PDF

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Publication number
WO2012081953A1
WO2012081953A1 PCT/MX2011/000154 MX2011000154W WO2012081953A1 WO 2012081953 A1 WO2012081953 A1 WO 2012081953A1 MX 2011000154 W MX2011000154 W MX 2011000154W WO 2012081953 A1 WO2012081953 A1 WO 2012081953A1
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Prior art keywords
copper
chalcopyrite
leaching
medium according
minerals
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PCT/MX2011/000154
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Spanish (es)
French (fr)
Inventor
Gretchen Terri Lapidus Lavine
Oscar Joaquín SOLÍS MARCIAL
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Universidad Autónoma Metropolitana
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Publication of WO2012081953A1 publication Critical patent/WO2012081953A1/en

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    • 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
    • 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

  • the present invention is related to the mining industry, for the treatment of minerals containing copper. Specifically it relates to an oxidative process for the extraction of copper, from ores of refractory mineral phases that contain it.
  • the present invention relates to the extraction of copper contained in refractory minerals and / or ores, and more specifically to the extraction of copper from refractory minerals and / or ores by an oxidation process with additive containing media. and complexers of ferric and cuprous ions.
  • this invention relates to the recovery of copper, i. and. metallic copper and / or copper compounds, from chalcopyrite and other ores that contain copper and also preferably contain sulfur.
  • One of the objectives of the present invention is to provide a leaching medium that increases the copper leaching rate of refractory ores or minerals that contain it. Another objective is to provide said medium that achieves an oxidative leaching medium.
  • the present invention teaches a technique that allows to reduce the formation of passivating solids, adding to the medium of customary sulfuric acid, acetone, alcohols or organic acids and organic nitriles.
  • the invention comprises the modification of the leaching solution for the dissolution of copper contained in sulphured mineral phases, which are not easily oxidizable (refractory).
  • the invention lies in contacting said mineral, with an acid solution containing complexing agents for cuprous and iron ions, stirring to promote oxidation of copper in solution.
  • Figure 1 shows the graph of the percentage of copper dissolution at 50 ° C, with and without the addition of acetone, of a mineral concentrate.
  • Figure 2 shows the graph of the percentage of copper dissolution at 50 ° C, with and without the addition of methanol, of a mineral concentrate.
  • Figure 3 shows the graph of the percentage of copper dissolution at 50 ° C, with the addition of acetic acid, of a mineral concentrate.
  • the oxidation of chalcopyrite is carried out in a medium that propitiates, on the one hand the complexation of copper (l) while preventing the formation of jarosites, by means of the affinity of the ice rro (lll) for compounds containing oxygen.
  • the chemical compounds that achieve the first purpose are acetonitrile (ACN), thiourea, thiosulfate and / or the chloride ion.
  • acetonitrile is preferred because of its chemical stability, relative to thiocomposites, and because it is not corrosive like the latter.
  • the present invention carries out the leaching of copper from mineral particles suspended in the medium described above, within a vessel or reactor with stirring.
  • the solution can be applied to columns or terraces constituted by the same material. After an adequate time has elapsed for the extraction, the depleted mineral is separated from the copper-containing solution, which is processed by methods commonly used in the field of hydrometallurgy.
  • the ores and minerals for which this process could be used are those that contain one or more refractory phases coppermade.
  • the term "mineral”, as used in the field, means a mineral phase (chalcopyrite or bornite) and the term “me- na "is used to refer to a mixture or aggregate of minerals.
  • the process of the present invention can be used with a ore or a mineral, as the material to be treated. Ores and / or minerals include sulphides. Some examples are Chalcopyrite, Bornite, and Covelita.
  • the process is carried out in an acidic medium.
  • Said medium preferably comprises sulfuric or hydrochloric acid, however other acids, such as acetic acid g I, can be used.
  • High concentrations of acid and complexing agents may be required to achieve high reaction rates in reducing the mineral phase, however, the process can be conducted at lower acid concentrations.
  • the process is operated at temperatures above 35 ° C, to promote the solubility of cupric sulfate and thus increase the rate of copper extraction.
  • the process of the present invention produces excellent results under such conditions.
  • it is not limited to these conditions; higher and lower temperatures and pressures are not excluded, and their use can increase the speed of the process, while the aqueous solution remains a liquid.
  • the product of the process of the present invention comprises a solution containing copper dissolved in its oxidation states (I) or (II) and from that form, the final metal values can be easily recovered.
  • copper (I) as Cu (ACN) 2 *
  • Copper (ll) as Cu 2 -. It is also important the presence of an organic nitrile that stabilizes copper in its oxidation state +1 and a highly soluble solvent in an acidic aqueous solution containing oxygen to avoid the precipitation of jarosites and iron oxides or hydroxides
  • the solution contained 82.4% of the copper that originally contained the concentrate.
  • the solid residue was mainly identified as iron oxides and unreacted chalcopyrite.
  • a copper extraction of only 11.8% was obtained.
  • Figure 1 they are shown Chalcopyrite copper extraction for both solutions with and without acetone.
  • the solution contained 68.1% of the copper originally contained in the concentrate.
  • the solid residue was identified primarily as unreacted chalcopyrite and iron oxyhydroxides.
  • a copper extraction of only 11.8% was obtained.
  • copper extraction from chalcopyrite is shown for both solutions with and without methanol.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to the mining industry, for the treatment of minerals containing copper. The invention specifically relates to an oxidative process for extracting copper from refractory mineral phases containing copper. The advantage of said means compared to prior art is that it increases the leaching speed. Said means for leaching copper from an ore or from at least one mineral that cannot be easily oxidised is characterised in that it comprises an acid solution containing copper(I) ion complexing agents and a solvent that prevents the formation of passivating phases.

Description

MEDIO PARA LA LIXIVIACIÓN DE COBRE DE MINERALES MEDIA FOR THE COPPER RELEASE OF MINERALS
REFRACTARIOS REFRACTORIES
CAMPO DE LA INVENCIÓN FIELD OF THE INVENTION
La presente invención está relacionada con la industria minera, de tratamiento de minerales que contengan cobre. Específicamente se relaciona con un proceso oxidativo para la extracción de cobre, a partir de menas de fases minerales refractarias que lo contengan . The present invention is related to the mining industry, for the treatment of minerals containing copper. Specifically it relates to an oxidative process for the extraction of copper, from ores of refractory mineral phases that contain it.
ANTECEDENTES DEL INVENTO BACKGROUND OF THE INVENTION
El presente invento se relaciona con la extracción de cobre contenidos en minerales y/o menas refractarios, y más especifica- mente a la extracción de cobre a partir de minerales y/o menas refractarios por un proceso de oxidación con medios que con- tengan aditivos y complejantes de iones férrico y cuproso. En una de sus modalidades preferidas, este invento se refiere a la recuperación de cobre, i. e. cobre metálico y/o compuestos de cobre, a partir de calcopirita y otras menas que contienen cobre y que también, preferentemente contienen azufre. The present invention relates to the extraction of copper contained in refractory minerals and / or ores, and more specifically to the extraction of copper from refractory minerals and / or ores by an oxidation process with additive containing media. and complexers of ferric and cuprous ions. In one of its preferred embodiments, this invention relates to the recovery of copper, i. and. metallic copper and / or copper compounds, from chalcopyrite and other ores that contain copper and also preferably contain sulfur.
La mayoría de las reservas mundiales de cobre se encuentra en fases sulfuradas. La estructura de dichos minerales los torna especialmente refractarios a la lixiviación oxidativa debido a la formación de capas pasivas de fases estables. Por esa razón, a la fecha el método más económico para extraer sus valores metálicos es mediante la fundición, un proceso de elevada tem- peratura que produce polvos y dióxido de azufre tóxico; se debe estabilizar este último compuesto, como ácido sulfúrico, para que el proceso cumpla con las normas ambientales. Most of the world's copper reserves are in sulphured phases. The structure of these minerals makes them especially refractory to oxidative leaching due to the formation of passive layers of stable phases. For that reason, to date the most economical method to extract its metallic values is by foundry, a high temperature process that produces toxic sulfur dioxide and powders; The latter compound, such as sulfuric acid, must be stabilized so that the process complies with environmental standards.
Durante las últimas cuatro décadas, se han investigado varias alternativas a la fundición, sobre todo por medio de fase acuosa que contiene agentes oxidantes. Sin embargo, la mayoría de las técnicas han involucrado temperaturas cercanas a la de ebullición de la solución, a presiones ambientales ó más elevadas. Una alternativa propuesta es el ataque bacterial del mineral, el cual oxida el azufre a sulfato, liberando los iones metálicos a la solución; desafortunadamente, dicha técnica es extremadamente lenta y es rentable únicamente para minerales de baja ley. Los intentos de oxidar las fases refractarias han enfrentado dificultades debidas a la pasivacion de las mismas fases por algunos de sus componentes, que impiden un alto porcentaje de extracción. Recientemente, el grupo de M. J. Nicol ha publicado una serie excelentes de artículos que reseña el estado del arte de la oxidación de calcopirita [Velásquez-Yévenes, L . , Nicol, M., Mikí, H., "The dissolution of chalcopyrite in chloride solutions. Part 1. The effect of solution potential", Hydrometallurgy, 103 (2010), 108-113; Velásquez-Yévenes, L., Miki, H . , Nicol, M., "The dissolution of chalcopyrite in chloride solutions. Part 2. Effect of var- ious parameters on the rate", Hydrometallurgy, 103 (2010), 80- 85; Nicol, M., Miki, H., Velásquez-Yévenes, L., "The dissolution of chalcopyrite in chloride solutions. Part 3. Mechanisms", Hydrometallurgy, 103 (2010), 86-95], en la cual se muestra que las especies responsables de la lenta extracción de cobre y la mejoría ganada con añadir a la solución especies catalizadoras, tales como plata. Por otro lado, Dixon y Tshilombo han solicitado una patente para el uso de pirita, suspendida junta con la calcopirita, en soluciones ácidas para aminorar la pasivacion de la superficie y acelerar la disolución del cobre contenido en la calcopirita [Dixon, D.G., Tshilombo, A.F., "Proceso de lixiviación para concentrados de cobre", MX PA06013742A, 27/11 /2006]. During the last four decades, several alternatives to smelting have been investigated, especially by means of an aqueous phase containing oxidizing agents. However, most of the techniques have involved temperatures close to the boiling point of the solution, at ambient or higher pressures. A proposed alternative is the bacterial attack of the mineral, which oxidizes sulfur to sulfate, releasing metal ions to the solution; Unfortunately, this technique is extremely slow and is profitable only for low grade minerals. Attempts to oxidize the refractory phases have faced difficulties due to the passivation of the same phases by some of their components, which prevent a high percentage of extraction. Recently, MJ Nicol's group has published an excellent series of articles that reviews the state of the art of chalcopyrite oxidation [Velásquez-Yévenes, L. , Nicol, M., Mikí, H., "The dissolution of chalcopyrite in chloride solutions. Part 1. The effect of solution potential", Hydrometallurgy, 103 (2010), 108-113; Velásquez-Yévenes, L., Miki, H. , Nicol, M., "The dissolution of chalcopyrite in chloride solutions. Part 2. Effect of var- ious parameters on the rate ", Hydrometallurgy, 103 (2010), 80-85; Nicol, M., Miki, H., Velásquez-Yévenes, L.," The dissolution of chalcopyrite in chloride solutions. Part 3. Mechanisms ", Hydrometallurgy, 103 (2010), 86-95], which shows that the species responsible for the slow extraction of copper and the improvement gained by adding catalyst species, such as silver, to the solution. On the other hand, Dixon and Tshilombo have applied for a patent for the use of pyrite, suspended together with the chalcopyrite, in acidic solutions to reduce the passivation of the surface and accelerate the dissolution of the copper contained in the chalcopyrite [Dixon, DG, Tshilombo, AF , "Leaching process for copper concentrates", MX PA06013742A, 11/27/2006].
No obstante lo anterior, a pesar de lograr porcentajes elevados de disolución de cobre con algunos métodos, el problema de la velocidad lenta de la extracción aún persistía, por lo que un proceso o un medio que lograra incrementar la velocidad de lixiviación de cobre seria merecedor de una patente al resolver un problema técnico en la industria, aún sin solución. Notwithstanding the foregoing, despite achieving high percentages of copper dissolution with some methods, the problem of the slow rate of extraction still persisted, so that a process or a means that could increase the copper leaching rate would be deserving of a patent when solving a technical problem in the industry, even without solution.
OBJETIVOS DE LA INVENCIÓN OBJECTIVES OF THE INVENTION
Uno de los objetivos de la presente invención es el de propor- cionar un medio lixiviante que eleve la velocidad de lixiviación de cobre de minerales o menas refractarios que lo contengan. Otro de los objetivos es proporcionar dicho medio que logre un medio lixiviante oxidativo. One of the objectives of the present invention is to provide a leaching medium that increases the copper leaching rate of refractory ores or minerals that contain it. Another objective is to provide said medium that achieves an oxidative leaching medium.
Y todos aquellos objetivos y ventajas que se harán aparentes con la lectura de la descripción y los ejemplos, que con fines ilustrativos más no limitativos, comprende ésta, And all those objectives and advantages that will become apparent with the reading of the description and the examples, which, for illustrative purposes rather than limitation, include this
BREVE DESCRIPCIÓN DEL INVENTO BRIEF DESCRIPTION OF THE INVENTION
La investigación relativa a los mecanismos de lixiviación y la indagación acerca de las causas de la pasivación, han indicado que la formación de covelita (CU2S2) y/o jarositas ocasiona la disminución en la velocidad de lixiviación de cobre a partir de la calcopirita [Nicol y col., supra ; Nava, D., González, I., Leinen, D., Ramos-Barrado, J.R., "Surface characterization by X-ray photoelectron spectroscopy and cyclic voltammetry of producís formed during the potentiostatic oxidation of chalcopyrite", 217th ECS eeting, Abstract #1361 , Abril, 2010]. Research related to leaching mechanisms and inquiring about the causes of passivation have indicated that the formation of covelite (CU2S2) and / or jarosites causes a decrease in the rate of copper leaching from chalcopyrite [Nicol et al., supra; Nava, D., González, I., Leinen, D., Ramos-Barrado, JR, "Surface characterization by X-ray photoelectron spectroscopy and cyclic voltammetry of producís formed during the potentiostatic oxidation of chalcopyrite", 217th ECS eeting, Abstract # 1361, April, 2010].
El presente invento enseña una técnica que permite disminuir la formación de los sólidos pasivantes, adicionando al medio de ácido sulfúrico acostumbrado, acetona, alcoholes o ácidos orgánicos y nitrilos orgánicos. En breve, el invento comprende la modificación de la solución lixiviante para la disolución de cobre contenidos en fases minerales sulfuradas, que no son fácilmente oxidables (refractarios). Específicamente, el invento radica en contactar dicho mineral, con una solución ácida que contiene agentes complejantes para los iones cuproso y de hierro, agitando para propiciar la oxida- ción del cobre en solución. The present invention teaches a technique that allows to reduce the formation of passivating solids, adding to the medium of customary sulfuric acid, acetone, alcohols or organic acids and organic nitriles. In short, the invention comprises the modification of the leaching solution for the dissolution of copper contained in sulphured mineral phases, which are not easily oxidizable (refractory). Specifically, the invention lies in contacting said mineral, with an acid solution containing complexing agents for cuprous and iron ions, stirring to promote oxidation of copper in solution.
BREVE DESCRIPCIÓN DE LAS FIGURAS BRIEF DESCRIPTION OF THE FIGURES
La Figura 1 muestra la gráfica del porcentaje de disolución de cobre a 50°C, con y sin la adición de acetona, de un concentrado mineral . Figure 1 shows the graph of the percentage of copper dissolution at 50 ° C, with and without the addition of acetone, of a mineral concentrate.
La Figura 2 muestra la gráfica del porcentaje de disolución de cobre a 50°C, con y sin la adición de metanol, de un concentrado mineral. Figure 2 shows the graph of the percentage of copper dissolution at 50 ° C, with and without the addition of methanol, of a mineral concentrate.
La Figura 3 muestra la gráfica del porcentaje de disolución de cobre a 50°C, con la adición de ácido acético, de un concentrado mineral . Figure 3 shows the graph of the percentage of copper dissolution at 50 ° C, with the addition of acetic acid, of a mineral concentrate.
DESCRIPCIÓN DETALLADA DE LA INVENCIÓN DETAILED DESCRIPTION OF THE INVENTION
La oxidación de calcopirita se lleva a cabo en un medio que propicie, por un lado la complejación de cobre(l) al mismo tiempo que evita la formación de jarositas, mediante la afinidad del hie- rro(lll) por compuestos que contienen oxígeno. Los compuestos químicos que logran el primer propósito son acetonitrílo (ACN), tiourea, tiosulfato y/o el ion cloruro. En el presente invento se prefiere el acetonitrílo debido a su estabilidad química, relativa a los tiocompuestos, y porque no es corrosivo como el último. Para incrementar la solubilidad del complejo Cu(ACN)2+ dentro del medio y a la vez inhibir la formación de los jarositas, se agrega un solvente altamente soluble en soluciones acuosas de ácido sulfúrico, como es la acetona, el etilenglicol, el ácido acé- tico, el acetáldehido, el metanol y el etanol. Como oxidante se utiliza sulfato cúprico y/ó peróxido de hidrógeno. Para aumentar la cinética inicial se agrega iones de plata, como enseña Nicol et al., supra. En una de sus modalidades, el presente invento lleva a cabo la lixiviación de cobre a partir de partículas mine- rales suspendidas en el medio arriba descrito, dentro de un recipiente ó reactor con agitación. Sin embargo, en principio se puede aplicar la solución a columnas ó terreros constituidos por el mismo material. Después de transcurrir un tiempo adecuado para la extracción, se separa el mineral agotado de la solución que contiene el cobre, la cual se procesa por métodos comunmente utilizados en el campo de la hidrometalurgia. The oxidation of chalcopyrite is carried out in a medium that propitiates, on the one hand the complexation of copper (l) while preventing the formation of jarosites, by means of the affinity of the ice rro (lll) for compounds containing oxygen. The chemical compounds that achieve the first purpose are acetonitrile (ACN), thiourea, thiosulfate and / or the chloride ion. In the present invention acetonitrile is preferred because of its chemical stability, relative to thiocomposites, and because it is not corrosive like the latter. To increase the solubility of the Cu (ACN) 2 + complex within the medium while inhibiting the formation of jarosites, a solvent that is highly soluble in aqueous solutions of sulfuric acid, such as acetone, ethylene glycol, acetic acid, is added tico, acetaldehyde, methanol and ethanol. As oxidant, cupric sulfate and / or hydrogen peroxide is used. To increase the initial kinetics, silver ions are added, as taught by Nicol et al., Supra. In one of its embodiments, the present invention carries out the leaching of copper from mineral particles suspended in the medium described above, within a vessel or reactor with stirring. However, in principle the solution can be applied to columns or terraces constituted by the same material. After an adequate time has elapsed for the extraction, the depleted mineral is separated from the copper-containing solution, which is processed by methods commonly used in the field of hydrometallurgy.
Las ineficiencias de los medios oxidantes previamente utilizados en la literatura y la práctica industrial, se superan por el medio propuesto en el presente invento, en el cual se disminuye la pa- sivación tanto de la calcopirita como de otras fases refractarias de cobre, como la covelita ( C u 2 S2) . Además la capacidad oxida- tiva se mantiene ó aumenta en el transcurso de la lixiviación debido a la oxidación del cobre(l) a cobre(ll) por el aire atmosférico. Las reacciones de oxidación de la calcopirita y covelita probablemente son las siguientes: The inefficiencies of the oxidizing media previously used in the literature and industrial practice are overcome by the means proposed in the present invention, in which the passivation of both chalcopyrite and other refractory copper phases, such as the covelite (C or 2 S 2 ). In addition the oxidation capacity tiva is maintained or increased during leaching due to the oxidation of copper (l) to copper (ll) by atmospheric air. The oxidation reactions of chalcopyrite and covelite are probably the following:
2CuFeS2 + 4Cu2 + + 8ACN → Cu2S2 + 4Cu(ACN)2 + + 2Fe + + 2S° Cu2S2 + 4Cu2+ + 12ACN → 6Cu(ACN)2 + + 2S° Nicol et al, supra, enseña que la segunda reacción (la oxidación de covelita) requiere una mayor capacidad oxidativa. También se puede lograr la oxidación con peróxido de hidrógeno. En cambio, el uso del Ion férrico (Fe(lll)) como oxidante, propicia mayor pa- sivación debido a la formación de jarositas ó oxihidróxidos, que recubren la superficie de la calcopirita u otra fase por oxidar y retarda su reacción. El presente invento se trata de adicionar, a la solución ácida, agentes complejantes (ligandos) que estabiliza el ion cuproso (Cu(l)) para forme un par redox con el ion cúprico y un solvente que impide la formación del precipitado. 2CuFeS 2 + 4Cu 2 + + 8ACN → Cu 2 S 2 + 4Cu (ACN) 2 + + 2Fe + + 2S ° Cu 2 S 2 + 4Cu2 + + 12ACN → 6Cu (ACN) 2 + + 2S ° Nicol et al, supra , teaches that the second reaction (the oxidation of covelite) requires a greater oxidative capacity. Oxidation with hydrogen peroxide can also be achieved. On the other hand, the use of ferric ion (Fe (lll)) as an oxidant, leads to greater passivation due to the formation of jarosites or oxyhydroxides, which cover the surface of the chalcopyrite or another phase to oxidize and delay its reaction. The present invention is about adding, to the acid solution, complexing agents (ligands) that stabilize the cuprous ion (Cu (l)) to form a redox pair with the cupric ion and a solvent that prevents the formation of the precipitate.
En general, como resultado de las investigaciones que permitieron concluir la materia que se pretende proteger mediante la presente solicitud de patente, se pudo constatar que las menas y minerales para los cuales se podría utilizar este proceso, son aquellos que contienen uno ó más fases refractarias de cobre. En general, el término "mineral", como se usa en el campo, significa una fase mineral (calcopirita ó bornita) y el término "me- na" se usa para referirse a una mezcla ó agregado de minerales. El proceso del presente invento puede usarse con una mena o un mineral, como el material a tratar. Las menas y/o minerales incluyen sulfuros. Algunos ejemplos son Calcopirita, Bornita, y Covelita. In general, as a result of the investigations that allowed to conclude the matter that is intended to be protected by this patent application, it was found that the ores and minerals for which this process could be used, are those that contain one or more refractory phases coppermade. In general, the term "mineral", as used in the field, means a mineral phase (chalcopyrite or bornite) and the term "me- na "is used to refer to a mixture or aggregate of minerals. The process of the present invention can be used with a ore or a mineral, as the material to be treated. Ores and / or minerals include sulphides. Some examples are Chalcopyrite, Bornite, and Covelita.
El proceso se lleva a cabo en un medio ácido. Dicho medio preferentemente comprende ácido sulfúrico ó clorhídrico, sin embargo se pueden usar otros ácidos, tal como ácido acético g I a - cial. Elevadas concentraciones de ácido y agentes complejantes (> 1 M) puede requerirse para lograr altas velocidades de reacción en la reducción de la fase mineral, sin embargo, se puede conducir el proceso a concentraciones de ácido más bajas. The process is carried out in an acidic medium. Said medium preferably comprises sulfuric or hydrochloric acid, however other acids, such as acetic acid g I, can be used. High concentrations of acid and complexing agents (> 1 M) may be required to achieve high reaction rates in reducing the mineral phase, however, the process can be conducted at lower acid concentrations.
Preferentemente el proceso se opera a temperaturas arriba de 35°C, para propiciar la solubilidad del sulfato cúprico y asi aumentar la velocidad de la extracción de cobre, En comparación con las técnicas anteriores, el proceso del presente invento produce excelentes resultados bajo tales condiciones. Sin embargo, no está limitado a estas condiciones; temperaturas y pre- siones mayores o menores no se excluyen, y su utilización puede incrementar la velocidad del proceso, mientras la solución acuosa permanece como un liquido. Preferably the process is operated at temperatures above 35 ° C, to promote the solubility of cupric sulfate and thus increase the rate of copper extraction. Compared to the prior art, the process of the present invention produces excellent results under such conditions. However, it is not limited to these conditions; higher and lower temperatures and pressures are not excluded, and their use can increase the speed of the process, while the aqueous solution remains a liquid.
El producto del proceso del presente invento comprende una so- lución que contiene cobre disuelto en sus estados de oxidación (I) ó (II) y a partir de esa forma, los valores metálicos finales pueden recuperarse fácilmente. Por ejemplo, el Cobre (I) como Cu(ACN)2* y Cobre(ll) como Cu2-. Es también importante la presencia de un nitrilo orgánico que estabilice el cobre en su estado de oxidación +1 y un solvente altamente soluble en una solución acuosa ácida que contenga oxigeno para evitar la pre- cipitación de jarositas y óxidos o hidróxidos de hierro The product of the process of the present invention comprises a solution containing copper dissolved in its oxidation states (I) or (II) and from that form, the final metal values can be easily recovered. For example, Copper (I) as Cu (ACN) 2 * and Copper (ll) as Cu 2 -. It is also important the presence of an organic nitrile that stabilizes copper in its oxidation state +1 and a highly soluble solvent in an acidic aqueous solution containing oxygen to avoid the precipitation of jarosites and iron oxides or hydroxides
EJEMPLOS EXAMPLES
Los siguientes ejemplos son representativos de los procesos en concordancia con el invento, pero no es de ninguna manera su intención limitar el concepto inventivo.  The following examples are representative of the processes in accordance with the invention, but it is in no way intended to limit the inventive concept.
Ejemplo 1 Example 1
Se colocaron 10 gramos de la fracción de +100 malla de un concentrado de calcopirita (22.5% Cu, 30.4% Fe, 7% Zn, 5% Pb y 32% S) con una solución de 140 mL de 2.5 M ácido sulfúrico, 60 mL de acetona, 20 gramos de sulfato cúprico pentahidratado, 20 mL de una solución acuosa de 1000 ppm plata como nitrato, 8 mL acetonitrilo y 10 mL de 30% peróxido de hidrógeno (H2O2), en un reactor de vidrio con condensación de vapores a la tempe- ratura de 50°C. Durante la lixiviación, se agitó la lechada para mantener las partículas en suspensión. Después de transcurrir dicho tiempo, la solución contenia el 82.4% del cobre que contenía el concentrado originalmente. El residuo sólido, fue identificado principalmente como óxidos de hierro y calcopirita sin re- accionar. En un experimento similar, sustituyendo los 60 mL de acetona con una cantidad igual de agua, se obtuvo una extracción de cobre solamente del 11.8%. En la Figura 1, se muestran la extracción de cobre de la calcopirita tanto para las soluciones con y sin acetona. 10 grams of the +100 mesh fraction of a chalcopyrite concentrate (22.5% Cu, 30.4% Fe, 7% Zn, 5% Pb and 32% S) were placed with a solution of 140 mL of 2.5 M sulfuric acid, 60 mL of acetone, 20 grams of cupric sulfate pentahydrate, 20 mL of an aqueous solution of 1000 ppm silver as nitrate, 8 mL acetonitrile and 10 mL of 30% hydrogen peroxide (H2O2), in a glass reactor with vapor condensation at the temperature of 50 ° C. During leaching, the slurry was stirred to keep the particles in suspension. After this time elapsed, the solution contained 82.4% of the copper that originally contained the concentrate. The solid residue was mainly identified as iron oxides and unreacted chalcopyrite. In a similar experiment, replacing the 60 mL of acetone with an equal amount of water, a copper extraction of only 11.8% was obtained. In Figure 1, they are shown Chalcopyrite copper extraction for both solutions with and without acetone.
Ejemplo 2 Example 2
Se colocaron 10 gramos de la fracción de +100 malla de un concentrado de calcopirita (22.5% Cu, 30.4% Fe, 7% Zn, 5% Pb y 32% S) con una solución de 140 mL de 2.5 M ácido sulfúrico, 60 mL de metanol, 20 gramos de sulfato cúprico pentahidratado, 20 mL de una solución acuosa de 1000 ppm plata como nitrato, 8 mL acetonitrilo y 10 mL de 30% peróxido de hidrógeno (H2O2), en un reactor de vidrio con condensación de vapores a la temperatura de 50°C. Durante la lixiviación, se agitó la lechada para mantener las partículas en suspensión. Después de transcurrir dicho tiempo, la solución contenía el 68.1% del cobre que con- tenía el concentrado originalmente. El residuo sólido, fue identificado principalmente como, calcopirita sin reaccionar y oxihidróxidos de hierro. En un experimento similar, sustituyendo los 60 mL de metanol con una cantidad igual de agua, se obtuvo una extracción de cobre solamente del 11.8%. En la Figura 2, se muestran la extracción de cobre de la calcopirita tanto para las soluciones con y sin metanol. 10 grams of the +100 mesh fraction of a chalcopyrite concentrate (22.5% Cu, 30.4% Fe, 7% Zn, 5% Pb and 32% S) were placed with a solution of 140 mL of 2.5 M sulfuric acid, 60 mL of methanol, 20 grams of cupric sulfate pentahydrate, 20 mL of an aqueous solution of 1000 ppm silver such as nitrate, 8 mL acetonitrile and 10 mL of 30% hydrogen peroxide (H2O2), in a glass reactor with vapor condensation at the temperature of 50 ° C. During leaching, the slurry was stirred to keep the particles in suspension. After this time elapsed, the solution contained 68.1% of the copper originally contained in the concentrate. The solid residue was identified primarily as unreacted chalcopyrite and iron oxyhydroxides. In a similar experiment, replacing the 60 mL of methanol with an equal amount of water, a copper extraction of only 11.8% was obtained. In Figure 2, copper extraction from chalcopyrite is shown for both solutions with and without methanol.
Ejemplo 3 Example 3
Se colocaron 10 gramos de la fracción de +100 malla de un con- centrado de calcopirita (22.5% Cu, 30.4% Fe, 7% Zn, 5% Pb y 32% S) con una solución de 140 mL de 2.5 M ácido sulfúrico, 60 mL de ácido acético, 40 mL de 30% peróxido de hidrógeno (H2O2), en un reactor de vidrio con condensación de vapores a la temperatura de 50°C. Durante la lixiviación, se agitó la lechada para mantener las partículas en suspensión. Después de transcurrir dicho tiempo, la solución contenia el 78,5% del cobre que contenía el concentrado originalmente. En la Figura 3, se muestran la extracción de cobre de la calcopirita tanto para las soluciones con y sin acetona. 10 grams of the +100 mesh fraction of a chalcopyrite concentrate (22.5% Cu, 30.4% Fe, 7% Zn, 5% Pb and 32% S) were placed with a solution of 140 mL of 2.5 M sulfuric acid , 60 mL of acetic acid, 40 mL of 30% hydrogen peroxide (H2O2), in a glass reactor with condensation of vapors at a temperature of 50 ° C. During leaching, the slurry was stirred to keep the particles in suspension. After this time elapsed, the solution contained 78.5% of the copper that originally contained the concentrate. In Figure 3, copper extraction from chalcopyrite is shown for both solutions with and without acetone.
Todas las publicaciones y solicitudes de patentes citadas en es- ta especificación se incorporan en la presente por referencia como si cada publicación ó solicitud de patente fuera señalada, específica y individualmente, para la incorporación por referencia. A pesar de que se describió en detalle el invento precedente mediante la ilustración y ejemplo con propósitos de claridad de entendimiento, será aparente a aquellos con experiencia en la técnica, en vista de las enseñanzas del presente invento, que puede hacerse ciertos cambios y modificaciones sin desviar del espíritu ó alcance de las reivindicaciones anexas. All publications and patent applications cited in this specification are hereby incorporated by reference as if each publication or patent application were designated, specifically and individually, for incorporation by reference. Although the preceding invention was described in detail by way of illustration and example for purposes of clarity of understanding, it will be apparent to those skilled in the art, in view of the teachings of the present invention, that certain changes and modifications can be made without deviate from the spirit or scope of the appended claims.

Claims

REIVINDICACIONES
1. Medio para la lixiviación de cobre a partir de menas ó uno ó más minerales refractarios que contengan un sulfuro ó sulfuros de cobre caracterizado por consistir en una solución ácida con agentes complejantes de iones cobre(l) y un solvente que evita la formación de fases pasivantes. 1. Means for leaching copper from ores or one or more refractory minerals containing a sulfide or copper sulphides characterized by consisting of an acid solution with complexing agents of copper (1) ions and a solvent that prevents the formation of passive phases
2. Medio según la reivindicación anterior, caracterizado porque el agente complejante es un nitrilo orgánico. 2. Medium according to the preceding claim, characterized in that the complexing agent is an organic nitrile.
3. Medio según la reivindicación anterior, caracterizado dicho medio, porque el nitrilo orgánico es acetonitrilo. 3. Medium according to the preceding claim, characterized in that said medium, because the organic nitrile is acetonitrile.
4. Medio según cualquiera de las reivindicaciones 1 a 3, en el cual el solvente es seleccionado del conjunto formado por acetona, alcoholes orgánicos y ácidos carboxilicos. 4. Medium according to any one of claims 1 to 3, wherein the solvent is selected from the assembly consisting of acetone, organic alcohols and carboxylic acids.
5. Medio según cualquiera de las reivindicaciones 1 a 4, en el cual la mena ó uno ó más minerales a lixiviar comprenden calcopirita, bornita, covelita, enargita o una combinación de éstos. 5. Medium according to any one of claims 1 to 4, wherein the ore or one or more minerals to be leached comprises chalcopyrite, bornite, covelite, enargite or a combination thereof.
6. Medio según la reivindicación anterior, en el cual la me- na ó el mineral consiste en calcopirita. 6. Medium according to the preceding claim, in which the mine or mineral consists of chalcopyrite.
7 Medio según cualquiera de las reivindicaciones 1 a 6, en el cual la solución ácida comprende ácido sulfúrico ó ácido clorhídrico. 7 Medium according to any of claims 1 to 6, in which the acid solution comprises sulfuric acid or hydrochloric acid.
PCT/MX2011/000154 2010-12-13 2011-12-09 Means for the leaching of copper from refractory minerals WO2012081953A1 (en)

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US11859263B2 (en) 2016-10-19 2024-01-02 Jetti Resources, Llc Process for leaching metal sulfides with reagents having thiocarbonyl functional groups
US11884993B2 (en) 2015-04-17 2024-01-30 Jetti Resources, Llc Process for leaching metal sulfides with reagents having thiocarbonyl functional groups

Non-Patent Citations (2)

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Title
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PARKER A. ET AL.: "An X-ray photoelectron spectroscopy study of the mechanism of oxidative dissolution of chalcopyrite", HYDROMETALLURGY, vol. 71, 2003, pages 265 - 276, XP004463199, DOI: doi:10.1016/S0304-386X(03)00165-8 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11884993B2 (en) 2015-04-17 2024-01-30 Jetti Resources, Llc Process for leaching metal sulfides with reagents having thiocarbonyl functional groups
US11859263B2 (en) 2016-10-19 2024-01-02 Jetti Resources, Llc Process for leaching metal sulfides with reagents having thiocarbonyl functional groups

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