Thèses sur le sujet « Pentlandit »

Non-oxidative acid leaching of pyrrhotite from Kevitsa’s Ni-concentrate and methods to recover by-products, have been investigated. Selective dissolution of pyrrhotite (Fe1-xS, 0<x<0.25) can enrich the content of the valuable metals, such as Ni and Co, in the final concentrate and will reduce the amount of Fe and S sent to the smelters. The pyrometallurgical smelting of leached concentrate will thus give less formation of smelter by-products in form of slag and SO2. The leaching was studied through an experimental design plan with parameter settings of  38.8% to 57.8% H2SO4 and temperatures from 60 to 100°C. The best results were obtained in experiments carried out at the lower experimental range. Leaching at 60°C with an initial acid concentration of 38.8% H2SO4 was found sufficient to selectively dissolve most of the pyrrhotite; leaving an enriched solid residue. A QEMSCAN analysis of the solid residue confirmed that most of the pyrrhotite had been dissolved and showed that pentlandite was still the main Ni-mineral. Chemical assays showed that more than 95% of the Ni, Co, and Cu remained in the final residue.    The utilized leaching process generates by-products, in the form of large quantities of Fe2+ in solution and gaseous H2S. To recover Fe2+, crystallization of iron(ii) sulfate (FeSO4∙nH2O) from leach solution through cooling have been studied. The crystallized crystals were further dehydrated into the monohydrate (FeSO4∙H2O) through a strong sulfuric acid treatment (80%H2SO4). XRD analysis confirmed that FeSO4∙H2O was the main phase in the final crystals, and a chemical analysis showed a Fe content of about 30%, 1.5% Mg, 0.4% Ca, and 0.2% Ni.    The possibility to leach the concentrate by circulating the acidic solution from the crystallization stage has been tested. The recirculation of the solution showed no negative effects, as the recoveries of elements and chemical assays of the final solid residue were found to be similar to the obtained assay when the concentrate was leached in a fresh solution.
Icke-oxidativ syralakning av magnetkis från Kevitsas Ni-koncentrat har studerats samt metoder för tillvaratagande av biprodukter. Genom en selektiv upplösning av magnetkis (Fe1-xS, 0<x<0.25) kan värdefulla metaller som Ni och Co anrikas i det slutliga koncentratet. Samtidigt som mängden Fe och S som skickas till smältverken minskar, vilket också innebär att mindre biprodukter i form av slagg och SO2 erhålls vid den pyrometallurgiska smältningen av Ni-koncentratet. En experimentell design plan genomfördes för att studera lakningen där syrakoncentrationen varierades från 38.8% till 57.8%H2SO4 och temperatur från 60 till 100°C. Bäst resultat erhölls vid de lägre parameterinställningarna. Lakning vid 60°C med en initial syrakoncentration på 38.8%H2SO4 visade sig vara tillräcklig för att selektivt lösa upp merparten av all magnetkis och lämna kvar en anrikad produkt. Via QUEMSCAN bekräftades att merparten av all magnetkis hade löst upp sig och att huvudsakligt Ni-mineral fortfarande var pentlandit. Kemiska analyser visade att mer än 95% av Ni, Co och Cu stannade kvar i fasta godset.    Den tillämpade lakningsmetoden genererar biprodukter i form av stora mängder Fe2+ i lösning och H2S i gasform. För att tillvarata Fe2+ har kristallisering av laklösning som järn(ii) sulfat (FeSO4∙nH2O) studerats genom kylning. De kristalliserade kristallerna avvattnades till monohydrat, FeSO∙1H2O, genom avvattning i stark svavelsyra (80%H2SO4). XRD bekräftade FeSO∙1H2O som huvudfas i slutliga kristallerna och kemisk analys visade på ca 30%Fe med huvudsakliga orenheter i form av 1.5% Mg, 0.4%Ca och 0.2% Ni.    Möjligheten till att laka i återcirkulerad lösning efter kristallisering har undersökts. Lakning i återcirkulerad lösning visade inga negativa effekter då liknande halter och utbyten erhölls till det fasta godset.

Hydrometallurgical processing of sulphide concentrates is an attractive method for the selective extraction of valuable metals. The dissolution of minerals in a leaching process involves several electrochemical parameters that need to be investigated• to ensure the development and growth of the base metal industry in South Africa. A study has been carried out to elucidate the leaching mechanism of a nickel-coppercobalt sulphide concentrate in an oxidative pressure-acid medium. The sulphide concentrate studied in this research, comprises mainly of the minerals pyrrhotite, (Fe1_xS) with x = 0 to 0.2, pentlandite, (Ni,Fe)9S8 and chalcopyrite, (CuFeS2). The leaching behaviour of these minerals was successfully studied by means of Atomic Absorption (AA) measurements, Scanning '•Electron Microscopy (SEM) and Moss bauer spectroscopy, after leaching took place in an oxidative pressure-acid medium. The dissolution of the valuable metals was achieved effectively with recoveries of well over 90% for nickel, copper and cobalt under the specific conditions studied. Mechanical activation by means of ultra fine milling improved metal extraction with an average of approximately 40%, after a leaching period of 150 minutes. The most suitable conditions for the oxidative pressure-acid leaching of the mechanically treated nickel-copper-cobalt sulphide concentrate in a dilute sulphuric acid medium were found to be: particle size 80% - 10J.Lm; temperature l10°C; oxygen partial pressure 10 bar; sulphuric acid concentration 30 kg/ton; solids content 15% by mass and an impeller agitation rate of 800 r/min. The values of the apparent activation energies of nickel, copper and cobalt, extracted from the sulphide concentrate, were found to be 20.6 (± 4.4) kJ/mol K, 33.6 (± 4.2) kJ/mol K and 17.4 (± 3.5) kJ/mol K respectively.
Thesis (MIng (Chemical Engineering))--Potchefstroom University for Christian Higher Education, 2001

Bibliography: leaves 139-146.
The present study has focused on exploring the extent to which metal ion activation occurs and influences flotation and how this can be managed so as to increase the separation of pentlandite from pyroxene and feldspar. The aim was to minimise the percentage pyroxene and feldspar reporting to the concentrate and simultaneously maximise the pentlandite recovery. The possible chemical reactions taking place on surfaces of synthetic pentlandite, natural pyroxene and feldspar were investigated at pH 4, 6 and 9 in di-sodium tetra borate solution and in synthetic process water in the case of zeta potential determinations, microflotation and ToF-SIMS (time of flight secondary ion mass spectrometry) analyses and in synthetic process water in the case of batch flotation tests.

Interaction with MgO-minerals is one mechanism suspected to reduce selectivity in flotation of pentlandite from ultramafic ore. Understanding the surface chemistry of the minerals involved will lead to improved flotation conditions that maximize flotation selectivity. The first part of the thesis compares isoelectric point (i.e.p.) and point of zero charge (p.z.c.) determined using Mular-Roberts [M-R] titration technique of MgO-minerals chlorite, serpentine and talc. The M-R technique was unsuccessful with talc, attributed to Mg2+ acting as potential determining ion. For serpentine and chlorite, respectively, p.z.c. was pH 4.3 and 4.6 and i.e.p. pH 3.2 and <3. Dispersion index (DI) for chlorite suggested that aggregation/dispersion is controlled by both; serpentine remained dispersed, possibly due to hydration effects.The second part determines surface properties of pentlandite and serpentine isolated from an ultramafic ore. Zeta potential measurements were made on minerals alone and as mixtures with either indifferent electrolyte or supernatant derived from an ore suspension as background. Individual mineral results anticipated interaction due to electrostatic attraction. This was confirmed in the mixed mineral case, with Mg(OH)2 precipitate interaction as an additional factor. Scanning electron microscopy validated the findings.Aggregation/dispersion was determined by turbidimetry using a light scattering technique and optical microscopy. The effect of selected factors on aggregation/dispersion of pentlandite and serpentine was investigated by a design of experiment (DOE). Concentration of carboxymethyl cellulose, CMC, and the interaction between CMC and pH were the important factors. Contact angle measurements explored effects of several factors on pentlandite hydrophobicity and, using a DOE, small-scale flotation was used to investigate effects on pentlandite floatability. The pH was the most important factor, acidic pH increasing both hydrophobicity and floatability. Copper activation enhanced both properties, as well; magnesium affected hydrophobicity at alkaline pH, but it did not show significant effect on floatability; serpentine was detrimental to the process; and CMC was capable of partially restoring the hydrophobicity and floatability of pentlandite depressed with serpentine.
L'interaction de la pentlandite avec des minéraux d'oxide de magnésium (MgO-) est soupçonnée d'être à l'origine de la sélectivité réduite de la pentlandite dans les procédés de flottation de minerais ultrabasiques. Une meilleure compréhension de la chimie de surface des minéraux impliqués devrait mener à l'amélioration des conditions de flottation qui en maximisent la sélectivité. La première partie de la thèse compare le point isoélectrique (p.i.e) et le point de charge nulle (p.c.n), déterminés à l'aide de la technique de titrage Mular-Roberts [M-R], de minéraux d'oxide de magnésium tels que la chlorite, la serpentine et le talc. Dans le cas du talc, la technique M-R a échoué, probablement dû aux ions Mg2+ qui jouent le rôle d'ions déterminateurs de potentiel. Dans le cas de la serpentine et de la chlorite, les p.c.n. ont été déterminés à pH 4,3 et 4,6 respectivement et les p.i.e à pH 3,2 et <3 respectivement. Des tests de décantations ont suggéré que l'agrégation/dispersion observée pour la chlorite était contrôlée à la fois par le p.c.n et le p.i.e ; la serpentine au contraire est restée dispersée, possiblement dû à des effets d'hydratation. La deuxième partie détermine les propriétés de surface de la pentlandite et de la serpentine isolées à partir d'un minerai ultrabasique. Des mesures du potentiel zêta ont été effectuées sur les minéraux seuls et mélangés en présence d'un électrolyte, indifférent dans un cas et surnageant dans l'autre cas, préparé à partir d'une suspension de minerai utilisée comme milieu d'étude. Les résultats relatifs aux minéraux individuels et en particulier les forces d'attraction électrostatique observables ont permis d'anticiper leur interaction. Cette hypothèse a été confirmée dans le cas des minéraux mélangés, étant après avoir pris en compte l'interaction de précipités de Mg(OH)2 comme facteur additionnel. Des observations au microscope électronique à balayage ont permis de valider les résultats. L'agrégation/dispersion a été déterminée par décantation en utilisant des techniques de lumière diffuse et de microscopie optique. L'effet de certains facteurs sur l'agrégation/dispersion de la pentlandite et de la serpentine a été étudié sur la base d'un plan d'expériences (PE). Entre autres, la concentration en carboxymethyl cellulose (CMC) et l'interaction entre le CMC et le pH ont été considérés comme des facteurs importants. Des mesures d'angle de contact ont permis d'explorer l'hydrophobicité de la pentlandite et, à l'aide d'un PE, une étude de flottation à petite échelle a été réalisée pour investiguer la flottabilité de la pentlandite. Les résultats ont montrés que le pH était le facteur le plus important, un pH acide ayant pour effet d'augmenter à la fois l'hydrophobicité et la flottabilité. L'ajout de cuivre a également permis de renforcer ces deux propriétés par un effet d'activation; la présence de magnésium au contraire a affecté l'hydrophobicité de la pentlandite à pH alcalin mais n'a pas eu d'effet significatif sur ses propriétés de flottabilité; la présence de serpentine s'est trouvée être préjudiciable au procédé mais l'utilisation de CMC a pu être utilisée afin de restaurer partiellement l'hydrophobicité et la flottabilité de la pentlandite diminuées par la présence de la serpentine.

Thesis (Ph.D. (Physics)) --University of Limpopo, 2013
The intention of the current study is to investigate structure, ion transport and reactivity of various forms of the cobalt pentlandite, Co9S8, at different temperatures using atomistic simulation methods with the support of electronic structure calculations. The first interatomic potentials of Co9S8 were derived with input data as structure and elastic properties from experiment and electronic structure calculations respectively. The potentials were validated by running energy minimization and molecular dynamics calculations. Structure, elastic properties and phonon spectra were well reproduced, together with the complex high temperature transformations and melting of Co9S8 as deduced from crystal structure, radial distribution functions, density profiles and diffusion coefficients. Amongst the high symmetry surfaces {111}, {101} and {101} atomistic surface energy calculations proposed the {111} surface of Co9S8 as the most stable in agreement with experimental morphologies, and water adsorption energies on the such surfaces which mostly agreed with those from electronic structure calculations. The structural and ion transport variations with temperature were investigated and predicted surface melting at lower temperatures than the bulk. The effects of hydration on the surfaces at low and high temperatures were also studied. The structural and ion transport properties of Co9S8 nanoparticles of varying sizes, covered by high symmetry surfaces {111}, {101} and {100} were predicted using molecular dynamics method based on our derived interatomic potentials. The structural and ion transport properties of Co9S8 nanoparticles of varying sizes, covered by high symmetry surfaces {111}, {101} and {100} were predicted using molecular dynamics method based on our derived interatomic potentials. Generally for {111}, {101} nanoparticles, high temperature transitions were abrupt for smaller nanoparticles and these tended to disintegrate and form voids. However, for larger nanoparticles the transitions were more gradual. Transitions in the {100} bound nanoparticles were less dramatic for all sizes and the formation of voids was reduced at high temperatures. Generally, the melting temperatures of different sizes of nanoparticles increases with the particle size hence approach the bulk limit. The interaction of nanoparticles with water was investigated.
Anglo Platinum, National Research Foundation (South Africa), and The Royal Society (UK)

The oxidation and ignition behaviour of the four major sulfide minerals present in the nickel concentrates smelted at the Kalgoorlie Nickel Smelter (KNS) has been established. These minerals are pyrite (FeS2), pyrrhotite (Fe1-nS, where n = 0 to 0.125), pentlandite ((FeNi)9S8) and violarite ( Ni2FeS4 ).The characteristic behaviour of these sulfides has been examined using Thermogravimetry-Differential Thermal Analysis (TG-DTA) under normal oxidation conditions ( l0ºC/min, air atmosphere). By increasing the heating rate to 40ºC/min and using an oxygen atmosphere, the tendency of the sulfides to ignite was established. Ignition was characterised by a highly exothermic reaction which occurred in association with a rapid mass loss over a short time span. Significant overheating of the samples beyond the temperature of the surroundings was observed. Pyrite, pyrrhotite and violarite all exhibited ignition behaviour while pentlandite did not.Using Isothermal Thermogravimetry (TG) the sulfides were subjected to shock heating conditions (heating rate = 3000-5000ºC/min, oxygen atmosphere) analogous to those which exist in an industrial flash smelter. The order of reactivity of the sulfides agreed with that observed during TG-DTA ignition trials. Even under these more intensely oxidising conditions pentlandite did not ignite. The effect of particle size on the ignition temperature was determined, larger particles igniting at a higher temperature. The magnitude of this effect varied according to the characteristics of the minerals.Products collected during Isothermal TG were examined by optical microscopy, Scanning Electron Microscopy (SEM) and Electron Probe Microanalysis (EPMA). Using these techniques it was possible to establish the morphology of the products and hence, to propose mechanisms for the reaction of the four sulfide minerals under ignition conditions.In order to ++
simulate the thermal environment which exists in the KNS, a pilot scale model of the reaction shaft was used. Nickel sulfide concentrates of varying mineralogy and particle size distribution were smelted under various conditions. The effect of larger particle size and increasing oxygen partial pressure on the reactivity of these concentrates was established.The products were quenched at the base of the shaft and collected for examination by optical microscopy, SEM and EPMA. Products ranged from unreacted to completely oxidised particles. The morphology and composition of these species were identified. Approximately 30 particles in each of 26 samples were examined with a view to establishing the frequency of occurrence of the particular product types in concentrates of differing mineralogy and particle size. This allowed proposals to be made regarding the fate of the individual sulfide minerals during ignition in the pilot scale flash reactor.

Bibliography: leaves 137-146.
This study examines the role complexing agents play in pentlandite-pyroxene flotation and focuses on the surface chemistry and interaction between valuable and gangue minerals as well as the interaction of complexing agents and reagents (xanthate, copper sulphate) in the system at pH 9. Microflotation, zeta potential measurements, ToF-SIMS analyses (time of flight secondary ion mass spectrometry) and X-ray photoelectron spectroscopy (XPS) were used as tools in determining the extent of surface alteration.

Small organic ‘collector’ ligands play an important role in the recovery of platinum group minerals (PGMs) from the industrial platinum mining process via the froth flotation process, which separates finely ground minerals on the basis of relative hydrophobicity. Design of novel ligands to improve PGM recovery is an ongoing industrial interest. This thesis involves the application of computational chemistry techniques to gain a first-principles understanding of simple mineral-collector ligand interactions, with a view to applying this understanding to the design of novel collector ligands. Experimental techniques are also used, where appropriate, to validate computational modelling in order to gauge the applicability of computational chemistry to this field. Sperrylite (PtAs2), the world’s most common PGM, was used as a model for a typical platinum group sulfide mineral. Pentlandite ((Fe,Ni)9S8) and pyrite (FeS2), two base metal sulfide minerals commonly associated with PGMs, were used as competitor surfaces to gauge collector selectivity. α-quartz (SiO2) was used as to model silicaceous waste material, and pure platinum (Pt) as an internal standard to gauge Pt-collector interactions. Chapter 1 provides an overview of PGM mining with particular focus on the froth flotation process. A brief overview of the computational methods applied in this work is provided in Chapter 2. Chapter 3 presents modelling work based on assessing the various mineral and metal surfaces upon which ligands adsorption is modelled. Stable ‘working surfaces’ are defined by calculating surface energies for various low Miller index cleavages of the bulk unit cells of these solids. Surface stability with respect to slab depth is also assessed. A number of methods, including application of the virtual crystal approximation, a pairwise cluster expansion and explicit site modelling, are used to resolve the issue of positional disorder of the metal sites in pentlandite. This leads to the observation that pentlandite slabs with a higher concentration of Ni atoms at the mineral/vacuum interface are more stable. A global minimum energy bulk unit cell of pentlandite is described. Chapters 4 and 5 deal with the adsorption of collector and aqua ligands onto these surfaces, with Chapter 5 also reporting attempts at rational in-silico ligand design. A novel method for calculating the binding energy of anionic species in periodic systems via a work-function based correction is described and tested for both mono- and dianionic species. Modelling of ethyl xanthate (H5C2OCS2-) and xanthate-based analogues (H5C2XCS2-, where X=N, NH, NC2H5, S, CH, CH2) shows a trend of increased binding strength upon formation of dianionic species. Whilst this observation was supported (to a lesser degree) by geometrical parameters, the extension of the work-function based correction to deal with dianionic species tended to significantly overbind these ligands and so the work function correction was found to be inappropriate for use in models with a charge state greater than -1. Modelling of heterocyclic ligands on selected surfaces shows weaker adsorption than non-heterocyclic species due to unfavourable electronic effects of the delocalised heterocycle on the R-CS2- head group. Efforts in ligand design focussed on optimising the electronic properties of the tail group in the xanthate structure to provide maximum electron density to the CS2- system. The output from this process was p-methoxyphenyl dithiocarbamate (H2CO-C6H4-N=CS2²-), which performed well in computational models. Synthesis of this ligand, as well as protonated Nethyl dithiocarbamate (H5C2NHCS2-) failed, however, due to the intrinsic instability of monosubstituted dithiocarbamates. Attempts to validate modelling results using two experimental techniques are reported in Chapter 6. Firstly, cyclic voltammetry experiments using sperrylite, pentlandite and platinum working electrodes suspended in collector solutions of concentration 1x10-3 M are reported, which show some correlation between the order of calculated binding energies and the relative position of the oxidation potential for the formation of disulfide oxidation products, a process which is affected by surface adsorption. Correlation is best for ethyl xanthate and diisobutyl dithiophospinate, but poor for N,N-diethyl dithiocarbamate ((H5C2)2NCS2-). Secondly, microflotation experiments for the recovery of sperrylite, pentlandite and pyrite using various collector ligands were conducted. Results broadly agree with prior microflotation literature, but show no simple correlation between ligand binding energies and flotation recovery, suggesting that more complex factors than simple ligand/mineral adsorption are involved.

This thesis examines the bioleaching of six different Canadian nickel sulphide ores at pH levels above what is generally considered optimum (~ 2). The majority of work discussed in this thesis was conducted with a low-grade metamorphosed ultramafic nickel sulphide ore from Manitoba, Canada (Ore 3), which is not currently exploitable with conventional technologies. The ore contains 21% magnesium and 0.3% nickel. Nickel is the only significant metal value, and is present primarily as pentlandite. A substantial fraction of the magnesium is present as the serpentine mineral lizardite, making processing difficult with conventional pyro- and biohydrometallurgical techniques. The work with this ore has two equally important objectives: to minimize magnesium mobilization and to obtain an acceptable level of nickel extraction. Batch stirred-tank bioleaching experiments were conducted with finely ground ore ( 147 µm) with temperature and pH control. The first phase of experimentation examined the effect of pH (2 to 6) at 30 °C, and the second phase examined all combinations of three pH levels (3, 4 and 5) and five temperatures (5, 15, 22.5, 30, and 45 °C).

Shelf tidal streams are accelerated by coastal features, such as headlands and islands. In the search for sustainable forms of electricity generation, such locations may become attractive for tidal stream power. For many prospective sites, however, little is known about the intricacies of the local tidal dynamics: knowledge which is crucial to understanding the resource and the potential environmental consequences of its extraction. This thesis explores tidal stream energy in the Pentland Firth (Scotland, UK). This channel contains some of the most promising tidal stream energy sites in the world and is set to become host to the first large-scale arrays of tidal stream turbines, but its detailed characteristics were previously unknown. A hydrodynamic model was used to investigate the complex tidal dynamics of the Pentland Firth. This demonstrated, for the first time, the hydrodynamic mechanisms driving the exceptionally fast tidal currents through this channel. The model was then refined at a key site within the Pentland Firth, the Inner Sound. The results provided insight into complex flow characteristics, such as displacement and misalignment of peak flood and ebb tides, which must be considered when contemplating the exploitation of this energy resource. Tidal stream turbines were simulated in the hydrodynamic model. Artificial energy extraction was parameterised at the sub-grid-scale via added seabed drag. Turbine drag of varying magnitude was represented by a novel analytical model based on published characteristics of horizontal axis turbines. This new formulation reflects the non-linear dynamics of tidal turbine operation. Using the new turbine model, arrays of turbines were simulated within the Inner Sound. Complex interactions between the dynamics of energy extraction and flow required individual turbines to be parameterised in-concert with all other turbines in the array. This required extra effort, but offered enhanced insight into the behaviour of turbine arrays. Accounting for nonlinear turbine dynamics at high current speeds limited the magnitude of peak energy dissipation. Tidal stream velocities decreased both upstream and downstream of the extraction zone and were accelerated around it. At peak energy extraction, changes in tidal velocity were detectable several kilometres from the array, but were confined to the shallow waters of the Inner Sound and its environs. Implications for array modelling are discussed in the context of environmental impact assessments.

This thesis investigates sublittoral epibenthic assemblages, the ecological processes associated with distributions of benthic assemblages and potential ecological impacts arising from the de-ployment of tidal energy devices (TEDs) at a key tidal energy development site. An extensive field campaign was undertaken to collect fine-scale, in-situ data for local hydrodynamics, seabed structure and epibenthic assemblages. Data from a two-dimensional hydrodynamic model com- plemented in-situ flow data and provided an insight into possible changes to local tidal patterns after the deployment of a tidal array. The study revealed a highly complex tidal stream structure with maximal velocities reaching 4.2 ms1 during spring tide. The seabed was predominantly formed by scoured bedrock. Deployment of a tidal array was predicted to decrease tidal flow within and downstream of the array by up to 24 % for peak flows, whereas effects on the seabed were thought to be minor. Epibenthic assemblages were typical for tide-swept channels with a fringe of dense kelp forest along the shallow, sheltered waters of the channel, followed by a 'tran- sition zone' dominated by foliose red algae in the mid-depth ranges and animal turf assemblages in the deeper, very tide-swept waters. Multivariate analyses identified depth and bed-shear stress as being strongly associated with the distribution and composition of assemblages. In conjunction with presence-only data for epibenthic species, depth and bed-shear stress were used as predic- tor variables to develop site-specific habitat suitability models (HSMs) for a baseline and TED deployment case. Comparison of probability of occurrence values between the respective HSMs indicated a potential increase of suitable habitat for species inhabiting the deep, very tide-swept circalittoral following the deployment of TEDs, whilst assemblages along the fringes of the channel were mostly unaffected. This is the first attempt of using HSM as a tool for identification of potential changes in distributions of benthic species arising from the deployment of TEDs. The good overall performance of the models shows this tool may be valuable for for impact analysis of tidal energy development projects.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Uma possibilidade para a recuperação de metais a partir de minerais com baixos teores ou de rejeitos industriais é a utilização da lixiviação com micro-organismos. A biolixiviação é o processo de oxidação bacteriana de sulfetos metálicos contendo metais de valor (por exemplo, níquel, cobre ou zinco), os quais são liberados para a solução, seguida da recuperação por técnicas metalúrgicas convencionais. Estudos de biolixiviação de concentrados de sulfetos minerais em tanques agitados e, sobretudo em pilhas, têm sido desenvolvidos em escala piloto e comercial. Entretanto, poucos trabalhos têm sido realizados sobre o aproveitamento de rejeitos minerais de processos convencionais, tais como flotação ou fusão em forno “flash”, por rotas biotecnológicas. O objetivo deste trabalho foi recuperar níquel e cobre de rejeitos industriais, provenientes de processo de flotação e de fusão, utilizando bactérias, especialmente da espécie Acidithiobacillus ferrooxidans ou pelo uso de soluções ácidas, em escala de laboratório. Também foram realizados experimentos de biolixiviação de um sulfeto de níquel (pentlandita) para avaliar o processo de solubilização do metal. Conjuntamente, outros experimentos foram realizados com a finalidade de se obter novas linhagens isoladas a partir destes rejeitos minerais. Suas diferenças fisiológicas foram avaliadas. A partir dos experimentos com os rejeitos encontrou-se que com a escória foi possível obter 13% de níquel e 8 % de cobre em solução após 14 dias de lixiviação biológica. Com soluções ácidas, em pH 0,5 e 1,0, as recuperações foram de 56% de níquel e 24% de cobre em pH 0,5 enquanto que em pH 1,0 as concentrações foram de 21% e 12% de niquele e cobre, respectivamente. Para a recuperação de níquel e cobre deste rejeito sugere-se a lixiviação ácida e não bacteriana. Com a lama as porcentagens...
Bacterial leaching is a feasible to recover metals from minerals with low grade or from mine wastes using microorganisms. The bioleaching process is the bacterial oxidation of valuables metals bearing sulphide minerals (e.g. nickel, copper or zinc), which are released to the solution, followed by conventional recovered by metallurgical techniques. Studies on bioleaching of sulphide minerals concentrates in stirred tanks and, particularly, in heaps, have been developed on pilot and commercial scales. However, few studies have been undertaken on using of mineral wastes from conventional processes such as flotation or flashing smelting through biotechnological routes. This work aims at recovering nickel and copper from industrial wastes such as flotation tailings and slag using bacteria, especially Acidithiobacillus ferrooxidans species, or using acid solutions at laboratory scale. Experiments were also accomplished for nickel sulfide bioleaching to evaluate the metal dissolution process, for comparison purpose. Other experiments were also carried out to obtain new strains isolated from mineral waste to study the physiological differences between them. After 14 days of bioleaching of slag it was possible to extract 13% of nickel and 8% of copper in solution while with acid solutions the extractions were 56% of nickel and 24% of copper at pH 0.5 and 21% and 12% at pH 1.0, respectively. For the metals solubilization from the slag it is suggested the acid leaching instead of bioleaching. With the flotation tailings the recoveries of nickel and copper were 23% e 16% at pH 0.5 or 1.0 while after 14 days with bioleaching the concentrations in solution were 46 % and 17% for nickel and copper. These results show that the flotation tailings can be treated with biological leaching for a higher recovery of metals. The studies of nickel sulfide bioleaching with different bacterial species reached only... (Complete abstract click electronic access below)

Resumo: Uma possibilidade para a recuperação de metais a partir de minerais com baixos teores ou de rejeitos industriais é a utilização da lixiviação com micro-organismos. A biolixiviação é o processo de oxidação bacteriana de sulfetos metálicos contendo metais de valor (por exemplo, níquel, cobre ou zinco), os quais são liberados para a solução, seguida da recuperação por técnicas metalúrgicas convencionais. Estudos de biolixiviação de concentrados de sulfetos minerais em tanques agitados e, sobretudo em pilhas, têm sido desenvolvidos em escala piloto e comercial. Entretanto, poucos trabalhos têm sido realizados sobre o aproveitamento de rejeitos minerais de processos convencionais, tais como flotação ou fusão em forno "flash", por rotas biotecnológicas. O objetivo deste trabalho foi recuperar níquel e cobre de rejeitos industriais, provenientes de processo de flotação e de fusão, utilizando bactérias, especialmente da espécie Acidithiobacillus ferrooxidans ou pelo uso de soluções ácidas, em escala de laboratório. Também foram realizados experimentos de biolixiviação de um sulfeto de níquel (pentlandita) para avaliar o processo de solubilização do metal. Conjuntamente, outros experimentos foram realizados com a finalidade de se obter novas linhagens isoladas a partir destes rejeitos minerais. Suas diferenças fisiológicas foram avaliadas. A partir dos experimentos com os rejeitos encontrou-se que com a escória foi possível obter 13% de níquel e 8 % de cobre em solução após 14 dias de lixiviação biológica. Com soluções ácidas, em pH 0,5 e 1,0, as recuperações foram de 56% de níquel e 24% de cobre em pH 0,5 enquanto que em pH 1,0 as concentrações foram de 21% e 12% de niquele e cobre, respectivamente. Para a recuperação de níquel e cobre deste rejeito sugere-se a lixiviação ácida e não bacteriana. Com a lama as porcentagens... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: Bacterial leaching is a feasible to recover metals from minerals with low grade or from mine wastes using microorganisms. The bioleaching process is the bacterial oxidation of valuables metals bearing sulphide minerals (e.g. nickel, copper or zinc), which are released to the solution, followed by conventional recovered by metallurgical techniques. Studies on bioleaching of sulphide minerals concentrates in stirred tanks and, particularly, in heaps, have been developed on pilot and commercial scales. However, few studies have been undertaken on using of mineral wastes from conventional processes such as flotation or flashing smelting through biotechnological routes. This work aims at recovering nickel and copper from industrial wastes such as flotation tailings and slag using bacteria, especially Acidithiobacillus ferrooxidans species, or using acid solutions at laboratory scale. Experiments were also accomplished for nickel sulfide bioleaching to evaluate the metal dissolution process, for comparison purpose. Other experiments were also carried out to obtain new strains isolated from mineral waste to study the physiological differences between them. After 14 days of bioleaching of slag it was possible to extract 13% of nickel and 8% of copper in solution while with acid solutions the extractions were 56% of nickel and 24% of copper at pH 0.5 and 21% and 12% at pH 1.0, respectively. For the metals solubilization from the slag it is suggested the acid leaching instead of bioleaching. With the flotation tailings the recoveries of nickel and copper were 23% e 16% at pH 0.5 or 1.0 while after 14 days with bioleaching the concentrations in solution were 46 % and 17% for nickel and copper. These results show that the flotation tailings can be treated with biological leaching for a higher recovery of metals. The studies of nickel sulfide bioleaching with different bacterial species reached only... (Complete abstract click electronic access below)
Orientador: Oswaldo Garcia Júnior
Coorientador: Denise Bevilaqua
Banca: Maria Lucia Gosales da Costa Araújo
Banca: Ana Teresa Lombardi
Banca: Wilson Cervi da Costa
Banca: Luis Gonzaga Santos Sobral
Doutor

In order to increase energy security and meet carbon emission reduction targets set by the EU and UK government, the UK energy sector has increased its reliance on renewable energy. The marine renewable sector is set to become a major contributor to the UK's energy portfolio but incumbent on the offshore renewable sector are the high development, operation and maintenance costs. Prevailing metocean conditions at an offshore energy site contribute significantly to the life-cycle costs of an offshore energy project. Where access to a site is limited by a lack of suitable weather-windows, leading to high instances of downtime, weather-induced costs increase. Determination of suitable metocean weather-windows, defined by maximum operating thresholds and the length of time required to perform a task can assist with the risk management of a project and the reduction of downtimes, thus reducing costs. Metocean weather-windows are determined using 31 years (the “climatological norm”) of ECMWF ERA-40 reanalysis data. The annual, seasonal and monthly distribution parameters for wind and wave regimes at three sites are derived, using three different distribution parameter estimation models. Probabilities of defined weather-windows are determined using the derived distribution parameters and compared with empirical probabilities, based on the frequentist approach. Wind regimes fit a Weibull distribution and wave regimes fit a 3P gamma distribution and unique annual, seasonal and monthly distribution parameters are required for accurate weather-window determination. When fitted to appropriate PDFs, the shape and scale values determined by the different estimation techniques result in significantly different probabilities. Empirical probabilities converge with those determined using the MLE model but both significantly differ from those derived using the LSM and MoM derived parameters. In the absence of a dataset spanning the climatological norm, this suggests that the MLE method of parameter estimation is more accurate for the successful determination of weather-windows.

La séquence plutonique du massif de Fizh (partie nord de l'ophiolite d'Oman) offre une complexité crustale, liée à une diversité des corps magmatiques et du système filonien. La cartographie détaillée montre une succession d'événements magmatiques dont les séries principales sont formées de gabbros lités, des wehrlites et pyroxénites, des gabbronorites. Le magmatisme gabbroïque est généré dans une grande chambre magmatique axiale, alors que le magmatisme wehrlitique est dit hors-axe ; ceci est conditionné par la segmentation axiale de la paléodorsale. L'asymétrie ainsi observée dans la séquence crustale est marquée par la distribution et l'abondance des corps ultrabasiques. Les variations longitudinales dans les séquences stratigraphiques montrent des discontinuités au sein de la paléodorsale dans ce massif. Les granitoïdes sous forme de filons ou de stocks, attestent une succession d'événements magmatiques et les modalités de l'accrétion. En effet, les plagiogranites sont liés à la cristallisation fractionnée des gabbros, au cours de l'épisode d'accrétion normale. Les granodiorites et les diorites quartziques sont rattachées spatialement aux ultrabasites et formées par cristallisation fractionnée pendant la phase d'écaillage intra-océanique. Les granites et les leucogranites sont tardifs et à cachet collisionnel. Ils sont issus de la fusion partielle de la semelle métamorphique et liés à l'épisode obductif chaud. Les gisements de chromite sont variés et sont localisés dans le manteau et à la limite manteau-croûte. Les concentrations de chromite dans les ultrabasites sont importantes et présentent un effet sur le comportement des éléments du groupe du platine. Les sulfures magmatiques (pentlandite et chalcopyrite) précipitent dans les wehrlites et les pyroxénites en même temps que le plagioclase. Le comportement des PGE dans les chromitites montre qu'elles sont moins différenciées que celles des autres massifs ophiolitiques. Les PPGE et particulièrement le Pd précipitent dans les ultrabasites en même temps que les sulfures d'origine magmatique

The geological history of the Early Palaeozoic in eastern Australia is not known precisely. The eastern margin of the outcropping Precambrian Craton 'Tasman Line' is poorly understood. The Thomson Orogen, which underlies much of eastern Queensland, lies to the east of the Tasman Line. Basement to the Tasman Orogenic Zone is poorly understood, but knowledge of this basement is critical to our understanding to the processes that formed the eastern margin of the Precambrian craton. The Lolworth-Ravenswood Province lies to the east of the Tasman Line in northeast Queensland. A study of basement terranes in the Lolworth-Ravenswood Province will therefore provide some insights as to the nature of crust beneath this area, and therefore to the basement to the Thomson Orogen. The Fat Hen Creek Complex comprises para-authchthonous bodies of granitoid within middle to upper amphibolite facies metamorphic rocks. Data contained herein demonstrate that the composition and geochemistry of the granitoid are compatible with the generation of the granitoid by partial anatexis of the metamorphic rocks that are part of the Cape River Metamorphics. Temperature and pressure of anatexis is determined to be between 800-850OC and 5-9kb. Under these conditions, experimental data indicate that meta-pelite and meta-greywacke will produce between 5-10% melt coexisting with biotite, cordierite, garnet and plagioclase. The mineralogy of the granitoid bodies in the Fat Hen Creek Complex is consistent with partial anatexis of meta-greywacke at these temperatures and pressures. 5-10% melt is generally insufficient to allow efficient separation of melt and restite. The granitoids of the Fat Hen Creek Complex are interpreted as being a closed system with melt generated during high-grade metamorphism not separating from the residium. U/Pb dating of zircon from the Fat Hen Creek Complex indicate two distinct periods of zircon growth. The older episode occurred during the Late Cambrian to Early Ordovician. A second episode is dated as Middle Ordovician. This younger age coincides with the onset of regional compression, and may be related to exhumation of a mid-crustal layer during thrusting. The Lolworth Batholith is one of three granite batholiths in the Lolworth-Ravenswood Province. It comprises mainly muscovite-biotite granite, with smaller areas of hornblende-biotite granite to granodiorite. Sills and dykes of muscovite and garnet-muscovite leucogranite extensively intrude both of these types. The hornblende-biotite granite to granodiorite is metaluminous, with petrographic and geochemical characteristics similar to the adjacent Ravenswood Batholith. U-Pb SHRIMP ages also overlap with those from the Ravenswood Batholith. ENd(tc) values of ~-3 suggest a significant crustal contribution in the magma. Zircon populations determined using the SHRIMP suggest some inheritance from a Neoproterozoic source. The two-mica granites make up over 80% of the batholith and show little variation throughout. Aluminium Saturation indices range dominantly from 1-1.1, in keeping with the muscovite-bearing nature of the granites. U-Pb ages are significantly younger than the hornblende-biotite granitoids. ENd(tc) is ~-10, suggesting a greater role for crustal material in these granites than in the hornblende-bearing varieties. Previously, these granites were interpreted as S-types, mainly on the basis of the presence of muscovite. Low Na/Ca and Na greater than K are both considered as indicators of source compositions and both are characteristic of a mafic igneous rather than a meta-sedimentary source. Anatexis of mafic igneous rocks at temperatures less than~1000OC are found experimentally to produce peraluminous melts similar to those which produced the two-mica granites. The third major rock-type in the Lolworth Batholith is muscovite leucogranite, which occurs as sills and dykes intruding older granites and basement. The age of the leucogranite was not determined, but it has sharp contacts with the two-mica granite suggesting that the latter had cooled prior to intrusion of the former. The leucogranite is strongly peraluminous and is deemed to have been derived from anatexis of a supra-crustal (meta-sedimentary) source. The batholith is therefore deemed to comprise three different elements. The hornblende-biotite granitoids are the western extension of the adjacent Ravenswood Batholith. The two-mica granite and muscovite leucogranite are derived from different sources, but may be part of the same crustal anatexis event. During the Early Palaeozoic, the Lolworth-Ravenswood Province saw the intrusion of three granite batholiths into a basement of Late Neoproterozoic to Cambrian meta-sedimentary rocks. Also, Late Cambrian to Early Ordovician and Middle Ordovician high-grade metamorphism accompanied by partial anatexis is recorded at several sites across northeast Queensland. Although this metamorphism is restricted to these sites, they are widespread across the area suggestive of a widespread metamorphic event at these times. Similar metamorphism is recorded in the Arunta Inlier in Central Australia increasing the possible extent of this event. The geochemistry, isotopic characteristics and zircon populations of granites in the Lolworth-Ravenswood Province are used to characterise their source rocks; and thus the basement to the Province. Precambrian basement is indicated to underlie the entire province. However, the source rocks for the eastern part of the Province (Ravenswood and into the Lolworth Batholiths) are different to source rocks for the western part of the Province. Georgetown-type crust extends eastwards from the outcropping area, extending under the western Lolworth-Ravenswood Province. Late Mesoproterozoic rocks are recorded from the Cape River area adjacent to the Lolworth Batholith. They are also indicated as source-rocks for granites in the Ravenswood Batholith. Rocks of this age are characteristic of Grenvillian-age mobile belts in the United States. Their presence in north Qeensland has implications for the breakup of Rodinia, the Mesoproterozoic-age super continent that broke up during the Neoproterozoic.

Previous research indicates compositional variation of pentlandite [(Fe,Ni)9S8] and the effect this variation may have on the electrochemical behaviour of pentlandite is poorly understood. Pentlandite is the primary source of nickel and an important base metal sulfide (BMS) in the platinum industry. It hosts significant amounts of PGEs especially palladium and rhodium when compared to chalcopyrite and pyrrhotite. The aim of the project was to investigate the possible compositional variations of natural pentlandite and the effect of these variations on the electrochemical behavior thereof. To study possible compositional variations, single pentlandite particles - in the order of 100μm in size from flotation concentrates (PGM deposits) and massive samples (massive ore bodies) - from various sources were employed. Electron microprobe analysis indicated a compositional variation of the pentlandite particles hand-picked from the flotation concentrate samples. Variation was observed in the cobalt, iron and nickel content and this was independent of the deposit. A slight compositional variation was observed from the massive pentlandite samples. The effect the compositional variation may have on the electrochemical reactivity of pentlandite was investigated using electrochemical techniques, i.e. measurement of the polarisation resistance and mixed potential as well as performing linear anodic voltammetry, current density–transients and electrochemical impedance spectroscopy (i.e. capacitance). Poor electrochemical response of the pentlandite microelectrodes was observed. Pre–existing pores, deep pores, cracks and the brittle nature of pentlandite microelectrodes may have contributed to the poor electrochemical response of natural pentlandite particles hand-picked from the flotation concentrate. Slight compositional variations of the massive pentlandite sample influenced the electrochemical behaviour. In aerated solutions, iron enriched pentlandites were less reactive after progressive oxidation. The lower reactivity of the electrodes was a result of thick oxide films formed. This was illustrated by polarisation resistance and capacitance measurements. The lower reactivity of the electrodes was also related to the mechanism of the reduction of oxygen at oxidised passive electrode surfaces. It is however difficult to distinguish if the differences in the reactivity was a result of the Fe/Ni ratio or the influence of cobalt. Current density transients confirmed that the reactivity of a pentlandite electrode to be time dependent. The reactivity of the electrode decreased during oxidation. A variation in the electronic properties of the formed oxide film was observed. Slight compositional variation of pentlandite did not have a significant effect on the rest potential values as do changes in the type of sulfides (e.g. pyrite vs. pentlandite). This was confirmed by similar rest potential values of various pentlandite electrodes. The oxidation of synthetic pentlandite may be influenced by the chemical composition. In de-aerated solutions, anodic oxidation (as indicated by the linear anodic voltammogram) of synthetic pentlandite started at a potential lower than of the natural electrodes. In aerated solutions, the synthetic pentlandite was less reactive and formed thicker oxide films. Copyright
Dissertation (MEng)--University of Pretoria, 2010.
Materials Science and Metallurgical Engineering
unrestricted

This thesis examines Barbara Pentland's relationship with feminist and gender issues as explored in her 1976 song cycle Disasters of the Sun. The first half of this thesis provides biographical information and some of Pentland's thoughts on being a woman composer in Canada. It briefly examines the collaboration between Pentland and the poet Dorothy Livesay and their relationship with the feminist movement in Canada. The latter half of this study is devoted to a detailed analysis of the seven songs in the cycle.

Barbara Pentland, one of Canada's foremost composers, is best known for her piano and chamber works. However, she composed for the voice throughout her career. The evolution of her compositional techniques is evident in her vocal works, which show post-romantic chromaticism, neo-classicism, serial techniques, aleatoric techniques and new explorations in sound. A study of Pentland's choice of poetry, and of the manner in which she sets the text, adds further insight into her compositional craft. This document analyzes the following songs: The Cottager To Her Infant (1929); Ruins (1932); Song Cycle 1. Wheat (1943) 5. Cities (1945); Three Sung Songs 2. Life 3. Let the Harp Speak (1964); Ballad for Soprano and Violin (1979); Ice Age (1986). They were chosen because they represent important stylistic periods, and demonstrate various influences on her writing.

This study explores the possibility of utilizing bioleaching techniques for nickel extraction from a mixed sulfide ore deposit with high magnesium content. Due to the ultramafic nature of this material, well-studied bioleaching technologies, which rely on acidophilic bacteria, will lead to undesirable processing conditions. This is the first work that incorporates nitrate-dependent bacteria under pH 6.5 environments for bioleaching of base metals. Experiments with both defined bacterial strains and indigenous mixed bacterial cultures were conducted with nitrate as the electron acceptor and sulfide minerals as electron donors in a series of microcosm studies. Nitrate consumption, sulfate production, and Ni released into the aqueous phase were used to track the extent of oxidative sulfide mineral dissolution; taxonomic identification of the mixed culture community was performed using 16S rRNA gene sequencing. Nitrate-dependent microcosms that contained indigenous sulfur- and/or iron-oxidizing microorganisms were cultured, characterized, and provided a proof-of-concept basis for further bioleaching studies.

Selective oxidation and sulfation roasting of nickel concentrate followed by leaching was investigated as a novel route for nickel production. In the oxidation roasting stage, the iron species in the nickel concentrate was preferentially oxidized to form iron oxides, leaving non-ferrous metals (Ni, Cu, Co) as sulfides. The roasted product was then sulfation roasted to convert the sulfides of the latter metals into water-soluble sulfates. The sulfates were then leached into solution for further recovery and separation from iron oxides. The oxidation of nickel concentrate was firstly studied by means of thermogravimetric and differential thermal analysis over a wide temperature range. A reaction scheme was deduced, in which preferential oxidation of iron sulfide species occurred over a wide temperature range up to about 700 ºC, forming a Ni1-xS core with iron oxide shell. A batch fluidized bed roaster was then constructed to study the oxidation and sulfation roasting of nickel sulfide concentrate. Oxidation roasting tests were carried out at temperatures between 650 °C and 775 °C. It was found that low temperatures (e.g. 650 °C) are favorable for the preferential oxidation of iron sulfide species while minimizing the formation of nickeliferous oxides, i.e. trevorite and NiO. Several parameters were varied in the sulfation roasting experiments, including the sulfation gas flowrate, sulfation roasting temperature, the addition of Na2SO4, sulfation roasting time, and the oxidation roasting temperature. Under optimized conditions of sulfation gas composition (95% air, 5% SO2), temperature (700 °C), Na2SO4 addition (10 wt%) and time (150 min), the conversions to sulfates were 79% Ni, 91% Cu, and 91% Co. Only 5% Fe forms water-soluble sulfate. The residue from the leaching of calcine in water contained 49% Fe and 10% Ni, which is a suitable feedstock for the production of ferronickel alloys. Therefore, further studies were also conducted to evaluate the reduction behavior of the residue with CO, H2 and graphite.