Wenying Liu

Associate Professor

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Dissertations completed in 2010 or later are listed below. Please note that there is a 6-12 month delay to add the latest dissertations.

Iodine-assisted heap leaching of chalcopyrite: laboratory and modelling studies (2022)

Copper mine operations face increasing challenges of processing low-grade chalcopyrite ores with elevated concentrations of impurities. Heap leaching is considered to be an effective and economically viable technology for treating these low-grade, complex copper sulfide ores. The addition of iodide in ferric sulfate solution is found to significantly enhance the dissolution of chalcopyrite at ambient temperatures. The aim of this research was to better understand the key factors that control the reaction rate and the mechanisms by which iodine accelerates the leaching kinetics. This research aim was achieved by conducting experimental and modelling studies of the iodine-assisted leaching of chalcopyrite concentrate and ore. Specifically, a series of leaching tests of increasing scale, from 50-mL bottle to 1-L reactor to 1-m and 6-m column tests, were carried out under partially- or fully-controlled leaching conditions; these leaching tests data were used to develop a kinetic model that correlates the copper extraction with the leaching conditions; the solid surface properties were examined by XRD, MLA, and XPS to uncover the leaching mechanisms; the calibrated kinetic model was finally used to assess the effect of key design and operating parameters on the performance of chalcopyrite dissolution in heap leaching.The experimental results show that the redox potential is the primary factor controlling the chalcopyrite leaching by controlling the iodine speciation in solution. Either diiodine or triiodide is considered to be the active oxidant responsible for chalcopyrite dissolution depending on the solution potential. The solid surface examination shows that the elemental sulfur and iron precipitates formed during leaching did not hinder the dissolution of chalcopyrite and that pyrite was inert during leaching. The kinetic model developed could simulate the copper extraction as a function of solution potential, total iodide concentration, and temperature. The sensitivity tests with the calibrated kinetic model show that the performance of the iodine-assisted leaching process can be improved by increasing irrigation rate, ferric concentration, iodide concentration, and temperature. The experimental and modelling results obtained in the present study can guide the design and implementation of the iodine-assisted heap leaching of chalcopyrite at an industrial scale.

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Sulfur deportment in nickel laterite calcination for ferronickel production via rotary kiln-electric furnace route (2021)

The rotary kiln-electric furnace (RK-EF) process is a common pyrometallurgical route for ferronickel production from nickel laterite ores. Sulfur is a harmful impurity that deteriorates the mechanical properties of nickel alloys. Due to the low sulfur content of the laterites, it is believed that the majority of the sulfur in crude ferronickel is originated from the process additives such as fuel and reductant in the rotary kiln. Therefore, it is crucial to investigate the effect of the sulfur content of the fuel on the calcine composition. Reducing sulfur absorption from the fuel to the calcine is beneficial to reduce the load of the refinery. This study investigates sulfur deportment in the nickel laterite calcination to obtain a fundamental understanding of the behavior of sulfur present in the rotary kiln fuel.In this work, the main reactions that occur in the calcination stage are identified. The kinetics of the reactions are investigated by combining model-free and model-fitting methods. The sulfurization reactions in the nickel laterite calcination are identified, and the main sulfur-containing compound in the calcine is found to be pyrrhotite (Fe7S8). Using coal with higher sulfur content, employing a more aggressive reducing atmosphere in the furnace, and increasing the gas flow rate result in an increase in the sulfur content of the calcine. Increasing temperature from 600 to 700 °C leads to higher sulfur deportation from the gas phase to the calcine. However, raising the temperature above 700 °C decreases sulfur deportation due to sintering of the particles and recrystallization of the silicate compounds. A comprehensive kinetic analysis on the sulfurization reactions revealed that the sulfurization reaction is diffusion-controlled and has a low activation energy of 1.4-5.3 kJ/mol. Using CaCO3 as a sulfur absorbent leads to 70.8-91% sulfur removal in the calcine. The effect of the processing temperature and time on reducing the sulfur content of the calcine are also investigated. Increasing time from 30 to 120 min results in decreasing sulfur removal from 91 to 78.3%. Raising temperature from 700 to 800 °C promotes sulfur removal; however, sintering of additive particles at above 800 °C reduces sulfur removal.

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Thermodynamic and kinetic limitations of gold leaching in ferric chloride media (2021)

The global gold industry is under increasing pressure to search for alternative technologies to replace cyanidation due to the inefficiency of cyanide in treating low grade refractory gold ores and increased public scrutiny on the use of cyanide in gold mining. Chloride has been identified as a promising candidate to replace cyanide. The objective of this research was to gain fundamental knowledge on the thermodynamic and kinetic limitations of gold dissolution in ferric chloride media at moderate temperatures. First, thermodynamic calculations were done to determine gold and iron speciation in chloride solution at varying initial ferric concentration, total chloride concentration, solution potential, and type of chloride salts. Then the effects of these variables on the kinetics of gold dissolution in ferric chloride media were studied by batch leaching and electrochemical tests using pure gold as the model mineral. Finally, the efficacy of ferric chloride media for gold leaching from real ores was tested by batch leaching of an oxide ore sample. The speciation calculation showed that gold dissolves as Au(I) species in ferric chloride solution and that the predominant ferric species is FeCl₂+, which was considered to be the main oxidizer. The batch leaching tests showed that the gold extraction increased with the initial ferric concentration up to 0.3 M; increasing total chloride concentration and the solution potential also had positive effects on gold dissolution; the kinetics of gold dissolution was significantly slower in the presence of the divalent salts. Gold extraction was thermodynamically controlled at low free chloride concentrations and low solution potentials. When these two variables were sufficiently high, the dissolution process was under kinetic control. The potentiodynamic tests revealed that the dissolution kinetics was cathodically controlled at ferric concentrations up to 0.3 M with sufficient chloride; while at sufficiently high ferric concentrations, the anodic process controlled the dissolution process, the kinetics of which increased with the total chloride concentrations. Gold was extracted from the oxide ore sample, but the drop in the solution potential led to a low overall extraction. The dissolution kinetics was enhanced by acid curing as pretreatment and increasing leaching temperature.

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Copper leaching in chloride media with a view to using seawater for heap leaching of secondary sulfides (2020)

Copper mines increasingly face the challenge of processing large amounts of low-grade sulfides of elevated concentrations of impurities. In most cases, the challenge is compounded by water scarcity. A potential strategy to address such challenge is to use seawater with elevated concentrations of chloride for heap leaching of secondary sulfides. To ensure success of such heap leach processes, we comprehensively investigated aqueous chloride solution properties at high ionic strength, kinetics of copper extraction from chalcocite in chloride media, and mechanisms by which various factors influence leaching rate, in both acidified ferric and cupric chloride media. The aqueous chloride solution properties were determined by thermodynamic calculations supported by laboratory ORP (oxidation-reduction potential) measurements. The leaching kinetics was quantified by conducting a series of reactor and column leaching tests under fully-controlled conditions. The mechanisms were uncovered using various surface characterization techniques, including SEM-EDX and XPS. The thermodynamic calculation determined the speciation of iron and copper at increasing chloride concentration up to 3 M, based on which the actual cathodic and anodic reactions responsible for copper extraction were proposed. The kinetics study showed that the leaching reaction slowed down after 70 – 80% of copper was extracted in both ferric and cupric chloride media at ambient temperature. Kinetic models were first developed to satisfactorily describe copper extraction as a function of ORP, chloride concentration, and temperature in reactors, and then scaled up to describe copper leaching performance in columns. The surface characterization results showed that sulfur sequentially transformed from monosulfide to disulfide, and then to polysulfide and elemental sulfur. The slow decomposition of polysulfide was responsible for the slow leaching at high ORPs, whereas a combination of polysulfide decomposition and diffusion barrier by elemental sulfur layer was the reason for the slow dissolution at low ORPs. The effect of chloride concentration on the reaction rate may only manifest itself at low ORPs where the level of the elemental sulfur crystallinity was lower. This body of knowledge would ultimately pinpoint possible options to optimize the leaching performance.

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Kinetics and mechanisms of arsenic release from amorphous and crystalline arsenic trisulfide (2020)

Preventing arsenic release from mine waste materials, i.e., source control, is a preferable option for controlling arsenic discharge to the environment. Designing effective source control strategies requires comprehensive knowledge on the leaching behavior of arsenic from its bearing minerals. To determine the kinetics and mechanisms of arsenic release, we carried out reactor leaching experiments using arsenic trisulfide (As₂S₃) as a model arsenic sulfide mineral. The experimental results show that the arsenic release increased with pH, the dissolved oxygen concentration, and temperature. The speciation analysis indicates that arsenic was present in solution in the form of arsenite (III) and arsenate (V) and that thiosulfate and sulfate were the main soluble sulfur species. A two-step process that involves a series of primary and secondary reactions was proposed to explain the release of different arsenic and sulfur species. The release rates of arsenic and sulfur from crystalline orpiment were always slower than those from amorphous As₂S₃. Kinetic equations were derived from the leaching data to describe the release rate as a function of the leaching parameters for both amorphous As₂S₃and crystalline orpiment. The magnitudes of the reaction orders and the activation energy indicate that the surface chemical reaction is limiting the rate of arsenic release from amorphous As₂S₃. In contrast, both kinetic modelling and the solid surface characterization support that a mixed-control mechanism determines the arsenic release from crystalline orpiment. Namely, the process is controlled by the surface chemical reaction and the diffusion of dissolved oxygen through a product layer on the solid surfaces. The solid surface characterization shows that this product layer is most likely to be an arsenic-deficient phase enriched in elemental sulfur.

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Master's Student Supervision

Theses completed in 2010 or later are listed below. Please note that there is a 6-12 month delay to add the latest theses.

An integrated machine learning approach for predicting the quantity and quality of mine waste rock drainage (2023)

Prediction of mine waste rock drainage is essential to waste rock management. In this research, multiple machine learning algorithms were integrated to predict the quantity and quality of waste rock drainage with regional weather data as the inputs: a tree-based algorithm to predict the occurrence of spring freshet, and two recurrent neural network algorithms to predict drainage flow rates and contaminant concentrations. The tree-based algorithms evaluated were decision tree, random forest, and AdaBoost; and the recurrent neural networks used were long short-term memory and gated recurrent unit. The machine learning approach developed was applied to a case study mine located in North America. The chemical constituents of interest (COIs) studied in this research were nitrate and selenium. Data, including 17-21 years of drainage flow rates data and 10-19 years of contaminant concentrations data, from three monitoring stations at the mine were used for the model training and validation. The data in the last monitoring year of the available dataset were assigned to the test set and the remaining data were assigned to the training set. According to the performance of all candidate algorithms, the random forest was selected for the prediction of spring freshet and the long short-term memory and the gated recurrent unit were used for the prediction of drainage flow rates and contaminant concentrations. The random forest algorithm was able to predict the occurrence of spring freshet with an accuracy of 91-95%. The long short-term memory and gated recurrent unit were capable of making robust predictions of the drainage flow rates and the contaminants concentrations. Assuming no significant changes in mining activities, this general approach may be capable of predicting the future loading of contaminants given the relevant weather data.

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Kinetic investigation of rare earth leaching on Labrador Canada rare earth ore in acidic sulphate medium (2023)

The kinetics of sulphuric acid leaching of rare earth elements in a sample from the Foxtrot deposit in Labrador, Canada was investigated. The selected parameters were, particle size fraction of +38 –53 µm, +53 -75 µm, +75 -106 µm, and +106 -150 µm, sulphuric acid concentration of 0.5 M, 1.5 M and 3 M, temperature of 30, 60, and 90 ℃. The highest extraction efficiency for Ce, Nd and Y was 96.72%, 84.91% and 72.83%, respectively at the highest temperature, highest sulphuric acid concentration and smallest particle size fraction. The highest selectivity was achieved at +106 -150 μm, temperature of 90 ℃, and sulphuric acid concentration of 0.5 M. It was determined that the kinetic experimental data followed the Jander product layer diffusion kinetic model, a type of shrinking core model, for all three elements. The activation energies for Ce, Nd, and Y were found to be 56.19 kJ/mol, 57.09 kJ/mol, and 38.57 kJ/mol, respectively. After identifying the most suitable kinetic model and calculating the activation energies, the rate orders were calculated for the mathematical model. These values were used to develop semi-empirical mathematical models for each element. The results showed that Y was the least affected by acid concentration and particle size, while Ce and Nd were the most affected. The acid leaching process resulted in crack and porosity formation for certain minerals but no notable change in particle size which is in a good agreement with the Jander kinetic model. The high activation energies with product layer diffusion control suggested that a mixed kinetic model might be in control of the leaching mechanism.

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The fundamental study of impurity behavior in wet chlorination of decopperized anode slime (2022)

The copper industry has been facing challenges associated with continuous declining ore grade and elevated levels of impurities in copper ores. Such challenges have already significantly impacted copper smelting and refining. The situation is compounded by increasingly complex feed materials processed by copper smelters. A major concern is the accumulation of impurity elements in copper anodes and the anode slimes generated in electrorefining. This, in turn, affects the downstream treatment of anode slimes for recovery of precious metals and platinum-group metals (PGMs) as valuable byproducts. Wet chlorination is hydrometallurgical process that involves the use of H₂O₂ and HCl for recovering these metals. The present study investigated the leaching behavior of not only gold and PGMs but also a range of impurity elements in the wet chlorination using both thermodynamic calculations and laboratory wet chlorination tests.The stable species of all elements present in the decopperized anode slime were identified in the Pourbaix diagram (Eh-pH diagrams) constructed. The results generally agreed with those reported in the literature, even though some species reported were not identifiable due to a lack of relevant thermodynamic data. The major findings of the laboratory wet chlorination tests were summarized as follows. Antimony played an important role in the behavior of impurity elements. The oxidation of antimony from Sb(III) to Sb(V) occurred in the ORP range of 600 - 700 mV, causing the precipitation of Sb(V) together with arsenic and bismuth as arsenato antimonates. The extractions of arsenic, antimony, bismuth, and tin were initially independent of but later affected by the rate of H₂O₂ addition due to the removal of antimony (V) from solution via precipitation of arsenato antimonates. The extraction of arsenic, antimony, bismuth, and tin increased with the leaching temperature. The extractions of arsenic, bismuth, and tin were affected by acidity but not by the total chloride concentration. However, the antimony extraction was affected by not only the proton concentration but also the chloride concentration. Simple alkaline leaching without H₂O₂ addition was shown to be possibly effective to remove some impurity elements, especially tellurium, arsenic, and tin, prior to the extraction of gold and PGMs.

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An investigation into determining the source of elevated metal concentrations in seepage at Mount Polley Mine (2020)

Unusual water chemistry coinciding with the appearance of a precipitate were observed in two seepages from a rock storage facility at Mount Polley Mine. This rock storage facility was originally characterized as non-acid generating, meaning that the rock under surface weathering/oxidizing conditions will not produce acid. However, these two seepages were not behaving according to drainage predictions and resembled a product of neutralized acid rock drainage. Due to the localized nature of the affected seepages, the cause of this unusual water chemistry was hypothesized to be the leakage of an external source of acid into the RSF. The possible acid sources were proposed to be an experimental lined heap leach pad and excess stockpiled elemental sulfur that had been sourced to provide the acid required for the heap leach pad. An inspection revealed that the heap leach pad liner appeared to be intact. However, drainage from the sulfur stockpile was insufficiently contained. By using bacteria culture experiments, bacterial DNA extraction, and bulk characterizations of the elemental sulfur, it was concluded that the sulfur had been oxidized, leading to the generation of sulfuric acid that infiltrated the underlying rock. To determine the extent to which the rocks had reacted with the acid generated from the sulfur stockpile, the rocks underneath the sulfur stockpile were sampled. Visual inspection and further laboratory analyses revealed extensive alteration of these rocks under acidic conditions, rendering them similar to leached oxide ore sampled from the experimental heap leach pad. pH-controlled weathering fronts were evident in these rocks, progressing from leached near the contact with the sulfur pile (pH 7). These altered rocks have been re-classified as PAG due to the depletion of carbonates from exposure to sulfuric acid. The findings of this research will help the mine assess the long-term stability of the altered rocks and guide future development of remediation strategies.

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Relationship between particle size distribution and porosity in dump leaching (2017)

Fluid flow is a critical process involved in the valuable metals extraction from low grade ore in heap and dump leaching as well as the release of harmful substances from waste rock piles. The mechanisms by which fluids move through the porous media depend on the fluid properties and the intrinsic properties of the porous media, with permeability being one critical factor. Particle size distribution is a key factor that affects permeability by forming pores of different structure and size. The objective of this research was to assess the particle size distribution in heterogeneous packed ore/rock beds and quantify the effect of particle size distribution on porosity. In the studied mine site, the particle size distribution in the dump leach pad was determined by analyzing aerial images of multiple dump faces taken by a drone. Particles spanned a wide range in size from less than 2 cm in diameter to larger than 2 m in diameter, with a P80 to be 2 m. The spatial segregation of fine particles and coarse particles along the dump faces was observed, which may contribute to the formation of preferential flow.The effect of particle size distribution on porosity was quantified by two methods: the bulk density and CT-imaging techniques. Porosities under three particle sorting conditions were studied: narrow-sized particles, poorly sorted particles and well sorted particles. For narrow-sized particles, the porosity measured by the bulk density method decreased as the particle size was increased up to 0.151 mm after which the porosity remained constant in the range tested. The influence of the particle size on the porosity for the well sorted particles was similar to that of the narrow-sized particles from both of the methods. For poorly sorted particles, in both methods, porosity decreased as the fraction of the fine particles added was increased to a certain value, after which the porosity started to increase as the fraction of fine particles was further increased. The results have important implications for metal extraction from run of mine ores using dump leaching and release of contaminants from waste rock piles by influencing fluid flow properties.

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