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Mechanism and kinetics of pyrite transformation at elevated temperatures

Aracena Alvaro, Jerez Oscar

Physicochemical Problems of Mineral Processing

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2021

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Vol. 57, iss. 6

127--139

EN

Pyrite (FeS2) is known as a sulfide that provides energy for various pyrometallurgical processes (fusion and conversion). There are several studies related to the evaluation of pyrite oxidation mechanisms at high temperatures, obtaining discrepancies in the products generated. In our work, the novelty of our research would be to obtain the thermochemical oxidation mechanism of FeS2 by using conventional thermogravimetric methods. The oxidative roasting of pyrite from 550 to 800°C was analyzed for an oxygen concentration of 5.07 to 28.06 kPa of oxygen and particle size between 12.3 to 33.8 microns. The results showed that the pyrite proceeded by sequential roasting: first, it produced an intermediate compound, pyrrhotite (Fe7S8), which was later oxidized to generate hematite (Fe2O3), both stages validated by weight loss of the sample as well as by analysis by DRX. Each stage had a different roasting speed as it was also influenced differently by different parameters. The temperature and particle size favored the rate of pyrrhotite generation, and the oxygen concentration favored the rate of hematite formation. The first-order kinetic equation ln (1-XPy) represented the roasting of the first stage (FeS2 → Fe7S8), with a calculated activation energy of 70.1 kJ/mol. The order of reaction was 0.5 concerning the partial pressure of oxygen and inversely proportional to the initial particle radius.

2

Uptake of copper ion using protonated dry alginate beads from dilute aqueous solutions

Aracena Alvaro, Álvarez César, Jerez Oscar, Guajardo Nadia

Physicochemical Problems of Mineral Processing

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2019

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Vol. 55, iss. 3

732--744

EN

This research aimed to identify the copper ion removal mechanism when using protonated dry alginate beads. This mechanism was explained through ion exchange between Cu ions and the protons from the functional groups of the alginate beads. Copper removal increased with stirring velocity, reaching values of 97.5 mg g-1 (97.5×10-3 kg/kg of PDAB) of dry alginate at 200 rev min-1, at a solution pH of 6.0 and a run time of 360 min. For the lowest level of copper concentrations, at 10 mg dm-3 (10×10-6 kg dm-3), full removal was attained. The removal kinetics was represented by a pseudo- first order model. A value of 0.0131 min-1 was found for the velocity constant. Under equilibrium conditions, the experiment data was fit to the Langmuir adsorption model, and the highest removal values were 270.3, 222.2 (222.2×10-3 kg/kg of PDAB) and 49 mg g-1 (49×10-3 kg/kg of PDAB) for pH values of 5.0, 3.5 and 2.5, respectively. These are higher than most sorbents used in the literature for copper removal. Increased temperature leads to higher Cu removal. The activation energy was calculated at 9.3 kJ mol-1 for the temperature range of 283 to 343K. Observations using SEM and composition measurements of the alginate cross-section taken by EDS showed a uniform distribution of the copper concentration through the structure of the alginate beads, independent of the solution pH, contact time and temperature.

3

Recovery of cobalt ions from diluted solutions by means of protonated dry alginate beads

Aracena Alvaro, Padilla Sebastián, Jerez Oscar

Physicochemical Problems of Mineral Processing

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2019

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Vol. 55, iss. 5

1286--1297

EN

Mining effluents contain cobalt ions that can damage humans and flora. However, this meta also has high commercial value when recovered. The objective of this research work was to recover cobalt (Co2+) from diluted solutions using a biosorbent, specifically protonated dry alginate beads (PDAB). Experimental work was carried out in batch from an initial concentration of 22×10-6 kg dm-3 Co2+ and 80 mg alginate. Variables such as agitation, pH solution, experimental time, isotherm values, and temperature were analyzed. Maximum cobalt recoveries were obtained at pH values above 5.0, reaching 60.6×10-3 kg kg-1 of PDAB. Cobalt recovery occurred with ion exchange mechanisms from alginate carboxyl group proton release. Experimental data had excellent fit with both the Lagergren kinetic model (pseudo-first order) and the Langmuir isotherm model. As temperature increased, cobalt recovery increased. The calculated activation energy was 12.8 kJ mol-1. Compositional measurements obtained by scanning electron microscope and energy-dispersive X-ray spectroscopy for alginate crosssections showed uniform distributions of cobalt concentrations throughout the spherical alginate structure, independent of solution pH, contact time, or temperature. Furthermore, elution gave significant cobalt re-extraction (98.2%) and demonstrated PDAB reusability.

4

Mechanism and leaching kinetics of molybdenite concentrate in a hydrogen peroxide-acid system

Aracena Alvaro, Azocar Alan, Ibáñez Juan Patricio, Jerez Oscar

Physicochemical Problems of Mineral Processing

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2019

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Vol. 55, iss. 1

140--152

EN

The mechanism and leaching kinetics of a molybdenite concentrate in a H2O2-H2SO4 system were studied. The experimental work was performed in a batch reactor equipped with a condenser, a mechanical agitator and a temperature control system. The effects of the temperature, H2O2 and H2SO4 concentrations, particle size, liquid/solid ratio and agitation speed on the Mo recovery were investigated. The thermodynamic results showed that the leaching mechanism it was governed by several intermediate reactions; however, the influences of sulfuric acid and passivation were not observed in the reaction. The most predominant experimental result was the maximum Mo recovery of 81.3% by leaching 64 μm particles at 333 K (60 °C) for 5400 s (90 min). The molybdenum recovery was generally enhanced by increasing the H2O2 and H2SO4 concentrations. However, at H2SO4 concentrations higher than 1.0 mol/dm3, the Mo recovery decreased. Although the agitation speed affected the Mo recovery considerably, high recoveries could be still obtained without mixing. The experimental results and XRD analysis confirmed the reaction mechanisms. The leaching kinetics were analyzed using a shrinking core model in which the rate was controlled by diffusion through a porous layer with radius ro. The reaction rate orders were 1.0 and 0.2 for the H2O2 and H2SO4 concentrations, respectively, and the rate was inversely proportional to the square of the initial particle radius. The calculated activation energy was 75.2 kJ/mol in the temperature range of 278-333 K (5-60 °C).

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Dissolution kinetics of secondary covellite resulted fromdigenitedissolutionin ferric/acid/chloride media

Aracena Alvaro, Espinoza Camila, Jerez Oscar, Carvajal Danilo, Jaques Aldonza

Physicochemical Problems of Mineral Processing

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2019

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Vol. 55, iss. 4

840--851

EN

Dissolution kinetics of digenite (Cu9S5) was studied in Fe3+-H2SO4-NaCl media. The temperature range for the study was between 297 and 373 K (24 and 100°C), with a ferric concentration between 0.0100 and 0.0806 mol/dm3, a sulfuric acid concentration of 0.05 to 1.5 mol/dm3 and a NaCl concentration of 1.5 to 5 mol/dm3. Agitation speed and particle size were also studied. Results indicate that the dissolution mechanisms of digenite occurs in two stages: i) generation of covellite (CuS) with the formation of cupric ion (Cu2+) and ii) dissolution of covellite (CuS) with copper production in the system, as well as amorphous sulfur (S°). The second stage occurred very slowly compared to the first stage, the above variables studied directly affected the second stage. Temperature, Fe3+ and H2SO4 concentration positively affected dissolution of covellite formed (second stage), while the presence of NaCl did not increase dissolution of Cu9S5 or CuS. Results showed that stirring speed had an important role in the dissolution rate of CuS. Dissolution kinetics was analyzed using the model of diffusion through the porous layer. Covellite dissolution reaction order was 2.3 and 0.2 with respect to the concentration of ferric and sulfuric acid, respectively, and the rate was inversely proportional to particle size. The calculated activation energy was 36.1 kJ/mol, which is a typical value for a reaction controlled by diffusion in the porous layer at temperature between 297 and 373 K (24 and 100°C).