Optimización de parámetros para la extracción de elementos desde minerales en medios ácido

[SPA] Esta tesis doctoral se presenta bajo la modalidad de compendio de publicaciones. Actualmente, la gran minería del cobre chilena se encuentra frente a nuevos problemas y desafíos a superar. El principal problema, es de carácter medio ambiental, debido a que la mayor parte de la producción es por procesos de flotación, lo que implica aumentar la generación de relaves, ocasionando drenajes ácidos que generan la movilidad de elementos pesados al medio ambiente. Otro desafío importante, es diversificar las extracciones de otros elementos (como ocurre actualmente con el molibdeno) para impulsar la exportación de productos básicos y aumentar el empleo. Además, se deben tratar recursos que hoy en día no se están aprovechando a escala industrial, un ejemplo son los minerales de cobre negro, estos recursos generalmente no se incorporan en las pilas de lixiviación. Estos minerales exóticos tienen cantidades considerables de Mn (aproximadamente 29%), lo que representa un atractivo comercial. Para abordar este desafío, se realizaron investigaciones a nivel laboratorio, de extracción de cobre y manganeso desde cobres negros mediante procesos de lixiviación. Se evaluaron diferentes aditivos y concentraciones de estos mediante la aplicación de modelos estadísticos de regresión cuadrática, evaluando efectos lineales, interacciones y curvaturas. Además, se diseñaron y probaron con éxito nuevos procesos de extracción. Finalmente, se pudo demostrar que para la disolución de Mn ya sea desde nódulos marinos o cobres negros, se obtienen resultados positivos al adicionar Fe en el sistema, siendo un parámetro óptimo de trabajo una razón de MnO2/Fe de 1/2, logrando extracciones sobre el 70% en tiempos de 20 min. Para la disolución de Cu desde sulfuros secundarios, se puede concluir que los mejores resultados se obtienen al trabajar a elevadas concentraciones de cloruro, siendo poco relevante la concentración de H2SO4. Por otra parte, para la disolución de calcopirita, trabajar en un medio clorurado incorporando altas concentraciones de MnO2 (razones de MnO2/CuFeS2 de 5/1) favorece el mantener un alto valor de potencial en el sistema, superando la pasivación de este mineral.[ENG] This doctoral dissertation has been presented in the form of thesis by publication. Currently, the great copper mining is facing new problems and challenges to overcome. The main problem is environmental, because most of the production is due to flotation processes, which implies increasing the generation of tailings, causing acid drains that generate the mobility of heavy elements to the environment. Another important challenge is to diversify the extractions of other elements (as is currently the case with molybdenum) to boost the export of basic products and increase employment. In addition, resources that are not currently being used on an industrial scale should be treated, an example is black copper ores, these resources are generally not incorporated into the extraction circuits or are not treated, whether in stocks, platforms leaching or waste. These exotic minerals have considerable amounts of Mn (approximately 29%), which represents a commercial appeal. To address this challenge, research was carried out at the laboratory level, for the extraction of copper and manganese from minerals through leaching processes. Evaluating different additives and concentrations thereof, applying the use of statistical models of quadratic regression, evaluating linear effects, interactions and curvatures. And in other cases, creating new extraction processes. Finally, it was discovered that for the dissolution of Mn either from marine nodules or black copper, very positive results are obtained by adding Fe in the system, an optimal working parameter being a ratio of MnO2/Fe of 1/2, achieving extractions above 70% in times of 20 min. For the dissolution of Cu from secondary sulphides, it was found that the best results are obtained when working at high concentrations of chloride, the concentration of H2SO4 being insignificant. On the other hand, for the dissolution of chalcopyrite, working in a chlorinated medium incorporating high concentrations of MnO2 (ratios of MnO2 / CuFeS2 of 5/1) favors maintaining a high potential value in the system, overcoming the passivation of this mineral.Scientific Equipment Unit- MAINI of the Universidad Católica del Norte (Chile)Los artículos que componen la tesis son los siguientes: Publicación 1: N. Toro*, M. Saldaña, E. Gálvez, M. Cánovas, E. Trigueros, J. Castillo and P. Hernández. “Optimization of Parameters for the Dissolution of Mn from Manganese Nodules with the Use of Tailings in an Acid Medium” Q2 ISI WoS. Minerals, 2019; https://doi.org/10.3390/min9070387. Publicación 2: N. Toro*, W. Briceño, K. Pérez, M. Cánovas, E. Trigueros, R. Sepúlveda and P. Hernández. “Leaching of Pure Chalcocite in a Chloride Media Using Sea Water and Waste Water” Q1 ISI WoS. Metals, 2019; https://doi.org/10.3390/met9070780. - Publicación 3: M. Saldaña, N. Toro*, J. Castillo, P. Hernández, E. Trigueros, and A. Navarra. “Development of an Analytical Model for the Extraction of Manganese from Marine Nodules” Q1 ISI WoS. Metals, 2019 https://doi.org/10.3390/met9080903. - Publicación 4: N. Toro*, K. Pérez, M. Saldaña, R. I. Jeldres, M. Jeldres and M. Cánovas. “Dissolution of pure chalcopyrite with manganese nodules and waste water” Q1 ISI WoS. Journal of Materials Research and Technology, 2019 https://doi.org/10.1016/j.jmrt.2019.11.020. - Publicación 5 (En Revisión): N. Toro*, W. Briceño, A. Navarra, K. Pérez, M. Cánovas and E. Trigueros. “Statistical and kinetic study for leaching of covellite in a chloride media” Q1 ISI WoS. Journal of Materials Research and Technology.Escuela Internacional de Doctorado de la Universidad Politécnica de CartagenaUniversidad Politécnica de CartagenaPrograma de Doctorado en Tecnología y Modelización en Ingeniería Civil, Minera y Ambienta

Statistical and kinetic study for leaching of covellite in a chloride media

Covellite is a relatively rare copper sulfide with slow dissolution kinetics. The present investigation used the surface optimization methodology to evaluate the effect of three independent variables (time, chloride concentration and sulfuric acid concentration) on the rate of extracting Cu from covellite. The effects of chloride concentration and temperature over time were also studied. An ANOVA indicated that the linear variables of time and chloride concentration have the greatest influence, this being highly representative (R2 = 0.9945). The highest copper extraction rate (71.23%) at room temperature, was obtained with a high chloride concentration (100 g/L), a low concentration of sulfuric acid (0.5 M), and a leaching period of 600 h. The dissolution is described by the model of the unreacted core, the rate of leaching of the covellite is controlled by the chemical surface reaction at temperatures between 50 and 90°C, with concentrations of 0.5 M of H2SO4, 100 g/L of chloride, and a leaching period of up to 6 hours, where an activation energy of 72.36 kJ/mol was obtaine.The authors are grateful for the contribution of the Scientific Equipment Unit-MAINI of the Universidad Católica del Norte for aiding in generating data by automated electronic microscopy QEMSCAN® and for facilitating the chemical analysis of the solutions. We are also grateful to Marina Vargas Aleuy and Carolina Ossandón Cortés of the Universidad Católica del Norte for supporting the experimental tests

A novel recycling route for spent li-ion batteries

In this work, a recycling route for spent Li-ion batteries (LIBs) was developed. For this, the recovery of the metal content in both electrodes (anode and cathode) was investigated. Based on these results, an economic analysis of this recycling process was carried out. The obtained results showed that more than 90% of the material contained in both electrodes was recycled. The dissolution with acetic acid of the metals present in the active cathodic material is thermodynamically viable and the addition of a reducing agent such as hydrogen peroxide improved the spontaneity of the reaction. Dissolutions close to 100% for Li and Co were obtained. In addition, it was determined that the synthesis of lithium and cobalt valuable compounds was viable from the leach liquor, recovering approximately 90% of Co as cobalt oxalate, and 92% of Li as lithium carbonate. Furthermore, carbon graphite and Cu were fully recovered (100%) from the anodes. Finally, the results of the economic analysis showed that the recovered products have a high commercial value and industrial interest, providing an environmentally and economically viable process.Fil: Pinna, Eliana Guadalupe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Toro, Norman. Universidad Arturo Prat; ChileFil: Gallegos, Sandra. Universidad Arturo Prat; ChileFil: Rodriguez, Mario Humberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; Argentin

Development of an analytical model for the extraction of manganese from marine nodules

Multivariable analytical models provide a descriptive (albeit approximate) mathematical relationship between a set of independent variables and one or more dependent variables. The current work develops an analytical model that extends a design of experiments for the leaching of manganese from marine nodules, using sulfuric acid (H2SO4) in the presence of iron-containing tailings, which are both by-products of conventional copper extraction. The experiments are configured to address the effect of time, particle size, acid concentration, Fe2O3/MnO2 ratio, stirring speed and temperature, under typical industrial conditions. The recovery of manganese has been modeled using a first order differential equation that accurately fits experimental results, noting that Fe2O3/MnO2 and temperature are the most critical independent variables, while the particle size is the least influential (under typical conditions). This study obtains representative fitting parameters, that can be used to explore the incorporation of Mn recovery from marine nodules, as part of the extended value chain of copper sulfide processing.The authors are grateful for the contribution of the Scientific Equipment Unit- MAINI of the Universidad Católica del Norte for aiding in generating data by automated electronic microscopy QEMSCAN®, and for facilitating the chemical analysis of the solutions. We are also grateful to the Altonorte Mining Company for supporting this research and providing slag for this study, and we thank Marina Vargas Aleuy, María Barraza Bustos and Carolina Ossandón Cortés of the Universidad Católica del Norte for supporting the experimental tests

Leaching of pure chalcocite in a chloride media using sea water and wastewater

Chalcocite is the most important and abundant secondary copper ore in the world with a rapid dissolution of copper in an acid-chloride environment. In this investigation, the methodology of surface optimization will be applied to evaluate the e_ect of three independent variables (time, concentration of sulfuric acid and chloride concentration) in the leaching of pure chalcocite to extract the copper with the objective of obtaining a quadratic model that allows us to predict the extraction of copper. The kinetics of copper dissolution in regard to the function of temperature is also analyzed. An ANOVA indicates that the linear variables with the greatest influence are time and the chloride concentration. Also, the concentration of chloride-time exerts a significant synergic e_ect in the quadratic model. The ANOVA indicates that the quadratic model is representative and the R2 value of 0.92 is valid. The highest copper extraction (67.75%) was obtained at 48 h leaching under conditions of 2 mol/L H2SO4 and 100 g/L chloride. The XRD analysis shows the formation of a stable and non-polluting residue; such as elemental sulfur (S0). This residue was obtained in a leaching time of 4 h at room temperature under conditions of 0.5 mol/L H2SO4 and 50 g/L Cl.The authors are grateful for the contribution of the Scientific Equipment Unit- MAINI of the Universidad Católica del Norte for aiding in generating data by automated electronic microscopy QEMSCAN® and for facilitating the chemical analysis of the solutions. We are also grateful to the Altonorte Mining Company for supporting this research and providing slag for this study, and we thank to Marina Vargas Aleuy and María Barraza Bustos of the Universidad Católica del Norte for supporting the experimental tests

Optimization of parameters for the dissolution of Mn from manganese nodules with the use of tailings in an acid medium

Manganese nodules are an attractive source of base metals and critical and rare elements and are required to meet a high demand of today’s industry. In previous studies, it has been shown that high concentrations of reducing agent (Fe) in the system are beneficial for the rapid extraction of manganese. However, it is necessary to optimize the operational parameters in order to maximize Mn recovery. In this study, a statistical analysis was carried out using factorial experimental design for the main parameters, including time, MnO2/Fe2O3 ratio, and H2SO4 concentration. After this, Mn recovery tests were carried out over time at di_erent ratios of MnO2/Fe2O3 and H2SO4 concentrations, where the potential and pH of the system were measured. Finally, it is concluded that high concentrations of FeSO4 in the system allow operating in potential and pH ranges (0.2 to 1.2 V and 1.8 to 0.1) that favor the formation of Fe2+ and Fe3+, which enable high extractions of Mn (73%) in short periods of time (5 to 20 min) operating with an optimum MnO2/Fe2O3 ratio of 1:3 and a concentration of 0.1 mol/L of H2SO4.The authors are grateful for the contribution of the Scientific Equipment Unit- MAINI of the Universidad Católica del Norte for aiding in generating data by automated electronic microscopy QEMSCAN®, and for facilitating the chemical analysis of the solutions. We are also grateful to the Altonorte Mining Company for supporting this research and providing slag for this study, and we thank Marina Vargas Aleuy, María Barraza Bustos and Carolina Ossandón Cortés of the Universidad Católica del Norte for supporting the experimental tests

Extraction of titanium from low-grade ore with different leaching agents in autoclave

The progressive depletion of primary sources to obtain metals has led to the search for alternative sources for their recovery. In the particular case of titanium, titaniferous sands are a viable option for obtaining this metal. This paper presents the results of the dissolution of titanium from titaniferous sands of Buenos Aires province (Argentina) in a laboratory autoclave (450 mL of capacity). The operating parameters studied were as follows: different acids (HF, H2SO4 and mixtures of these acids); leaching agent concentration, 5–20% v/v; temperature, 75–150 ◦C; time, 30–180 min; solid–liquid ratio, 0.9–3.6% w/v; stirring speed, 110–550 rpm. The obtained results indicate that the increase in the leaching agent(s) concentration, temperature and time of contact with the acid mixtures have a marked effect on the dissolution reaction of titanium. Optimal conditions to achieve 89% extraction of titanium were obtained by leaching at 123 ◦C, 330 rpm, 80 min and 1.8% w/v with a mixture of 15% HF (v/v) and 10% H2SO4 (v/v).Fil: Rodriguez, Mario Humberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Rosales, Gustavo Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Pinna, Eliana Guadalupe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Tunez, Fernando Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Toro, Norman. Universida Arturo Prat; Chile. Universidad Católica del Norte; Chile. Universidad Politécnica de Cartagena; Españ

Optimization of the Heap Leaching Process through Changes in Modes of Operation and Discrete Event Simulation

The importance of mine planning is often underestimated. Nonetheless, it is essential in achieving high performance by identifying the potential value of mineral resources and providing an optimal, practical, and realistic strategy for extraction, which considers the greatest quantity of options, materials, and scenarios. Conventional mine planning is based on a mostly deterministic approach, ignoring part of the uncertainty presented in the input data, such as the mineralogical composition of the feed. This work develops a methodology to optimize the mineral recovery of the heap leaching phase by addressing the mineralogical variation of the feed, by alternating the mode of operation depending on the type of ore in the feed. The operational changes considered in the analysis include the leaching of oxide ores by adding only sulfuric acid (H2SO4) as reagent and adding chloride in the case of sulfide ores (secondary sulfides). The incorporation of uncertainty allows the creation of models that maximize the productivity, while confronting the geological uncertainty, as the extraction program progresses. The model seeks to increase the expected recovery from leaching, considering a set of equiprobable geological scenarios. The modeling and simulation of this productive phase is developed through a discrete event simulation (DES) framework. The results of the simulation indicate the potential to address the dynamics of feed variation through the implementation of alternating modes of operation.This research received no external funding

Viscoelasticity of Quartz and Kaolin Slurries in Seawater: Importance of Magnesium Precipitates

In this study, the viscoelastic properties of quartz and kaolin suspensions in seawater were analysed considering two distinct conditions: pH 8 and 10.7. Creep and oscillatory sweep tests provided the rheological parameters. An Anton Paar MCR 102 rheometer (ANAMIN Group, Santiago, Chile) was used with a vane-in-cup configuration, and the data were processed with RheoCompass (TM) Light software (ANAMIN Group, Santiago, Chile). The outcomes were associated with the formation of solid species principally composed of magnesium precipitates. The magnesium in solution reduced in the presence of quartz (68 wt %), from 1380 to 1280 mg/L. Since the difference was not large regarding the solid-free seawater, the disposition of solid complexes at pH 10.7 was expected to be similar. The jump in pH caused both yield stress and viscoelastic moduli to drop, suggesting that the solid precipitates diminished the strength of the particle networks that made up the suspension. For the kaolin slurries (37 wt %), the yield stress raised when the pH increased, but unlike quartz, there was significant adsorption of magnesium cations. In fact, the concentration of magnesium in solution fell from 1380 to 658 mg/L. Dynamic oscillatory assays revealed structural changes in both pulps; in particular, the phase angle was greater at pH 8 than at pH 10.7, which indicates that at more alkaline conditions, the suspension exhibits a more solid-like character.Ricardo I. Jeldres thanks Conicyt Fondecyt 11171036 and Centro CRHIAM Project Conicyt/Fondap/15130015. The authors are grateful for the contribution of the Scientific Equipment Unit—MAINI of the Universidad Católica del Norte for facilitating the XRD analysis. Pedro Robles thanks the Pontificia Universidad Católica de Valparaíso for the support provided. This research was funded by Conicyt Fondecyt 11171036 and Centro CRHIAM Project Conicyt/Fondap/1513001

Extraction of Mn from Black Copper Using Iron Oxides from Tailings and Fe2+ as Reducing Agents in Acid Medium

Exotic type deposits include several species of minerals, such as atacamite, chrysocolla, copper pitch, and copper wad. Among these, copper pitch and copper wad have considerable concentrations of manganese. However, their non-crystalline and amorphous structure makes it challenging to recover the elements of interest (like Cu or Mn) by conventional hydrometallurgical methods. For this reason, black copper ores are generally not incorporated into the extraction circuits or left unprocessed, whether in stock, leach pads, or waste. Therefore, to dilute MnO2, the use of reducing agents is essential. In the present research, agitated leaching was performed to dissolve Mn of black copper in an acidic medium, comparing the use of ferrous ions and tailings as reducing agents. Two samples of black copper were studied, of high and low grade of Mn, respectively, the latter with a high content of clays. The effect on the reducing agent/black copper ratio and the concentration of sulfuric acid in the system were evaluated. Better results in removing Mn were achieved using the highest-grade black copper sample when working with ferrous ions at a ratio of Fe2+/black copper of 2/1 and 1 mol/L of sulfuric acid. Besides, the low-grade sample induced a significant consumption of H2SO4 due to the high presence of gangue and clays.The authors are grateful for the contribution of the Scientific Equipment Unit- MAINI of the Universidad Católica del Norte for aiding in generating data by automated electronic microscopy QEMSCAN® and for facilitating the chemical analysis of the solutions. We are also grateful to the Altonorte Mining Company for supporting this research and providing slag for this study, and we thank to Marina Vargas Aleuy and María Barraza Bustos of the Universidad Católica del Norte for supporting the experimental tests. Also, we Conicyt Fondecyt 11,171,036 and Centro CRHIAM Project Conicyt/Fondap/15130015. This research received no external fundin