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In order to increase the current efficiency in copper electrowinning tankhouses, iron can be removed from the electrolyte using ion exchange. While this is a proven technology, very little data is available for the application of this technology to copper electrowinning electrolytes containing antimony and bismuth. The feasibility of utilizing iron ion exchange for the removal of iron from copper electrowinning electrolytes containing antimony and bismuth was studied in the laboratory. A picolylamine, a sulphonated diphosphonic, an aminophosphonic and three sulphonated monophosphonic resins were tested. The picolylamine resin was found to be completely impractical as it loaded high levels of copper. All the phosphonic resins tested loaded an appreciable amount of antimony, however, only the aminophosponic resin loaded an appreciable amount of bismuth. Tests to determine whether or not the sulphonated monophosphonic Purolite 5957 resin would continue to load antimony with time and, hence, reduce the resin's ability to remove iron gave inconclusive results. In the event that the resin's ability to remove iron is hampered due to antimony loading, testing has shown that the resin performance may be restored via a regeneration with a solution containing sulphuric acid and sodium chloride. A case study for the application of this technology to the CVRD Inco CRED plant has shown that, while iron removal by ion exchange is technically feasible, it will upset the plant's acid balance in electrolyte. Therefore, an acid removal process would need to be implemented in tandem with an iron ion exchange system. Additionally, preliminary calculations suggest that a system with a single ion exchange column may have difficulty removing sufficient iron for the CRED design conditions. Therefore, consideration should be given to the possibility of utilizing a two column system (one column loading, one column stripping).

In order to increase the current efficiency in copper electrowinning tankhouses, iron can be removed from the electrolyte using ion exchange. While this is a proven technology, very little data is available for the application of this technology to copper electrowinning electrolytes containing antimony and bismuth. The feasibility of utilizing iron ion exchange for the removal of iron from copper electrowinning electrolytes containing antimony and bismuth was studied in the laboratory. A picolylamine, a sulphonated diphosphonic, an aminophosphonic and three sulphonated monophosphonic resins were tested. The picolylamine resin was found to be completely impractical as it loaded high levels of copper. All the phosphonic resins tested loaded an appreciable amount of antimony, however, only the aminophosponic resin loaded an appreciable amount of bismuth. Tests to determine whether or not the sulphonated monophosphonic Purolite 5957 resin would continue to load antimony with time and, hence, reduce the resin's ability to remove iron gave inconclusive results. In the event that the resin's ability to remove iron is hampered due to antimony loading, testing has shown that the resin performance may be restored via a regeneration with a solution containing sulphuric acid and sodium chloride. A case study for the application of this technology to the CVRD Inco CRED plant has shown that, while iron removal by ion exchange is technically feasible, it will upset the plant's acid balance in electrolyte. Therefore, an acid removal process would need to be implemented in tandem with an iron ion exchange system. Additionally, preliminary calculations suggest that a system with a single ion exchange column may have difficulty removing sufficient iron for the CRED design conditions. Therefore, consideration should be given to the possibility of utilizing a two column system (one column loading, one column stripping).

In hydrometallurgical copper production plants, titanium-based electrodes coated with a conductive layer of IrO2-Ta2O5 are widely used as anodes in acidic copper electrowinning baths because of their long service life and low overpotential for oxygen evolution. The presence of trace amounts of ions such as fluoride, aluminum, and iron in sulfate-based electrowinning baths is believed to affect the stability of IrO2-Ta2O5 coated anodes. Hence, in this study, the effect of fluoride and metallic cations on the lifetime of IrO2-Ta2O5 coated Ti electrodes in sulfuric acid solutions has been investigated, and a degradation mechanism for IrO2-Ta2O5 coatings in the presence of fluoride has been proposed. Typical lifetime of the conductive ceramic coated anodes is 1 to 2 years. In order to predict electrode performance over this long period, an accelerated laboratory test that can be carried out in a few weeks is often used. This test, known as accelerated lifetime test (ALT), is conducted by electrically stressing the anodes at a current density that is much higher than the current density used for electrowinning while monitoring the change in the cell potential. The time required for the cell voltage to increase by 5 V is taken as the accelerated lifetime of the oxide electrode. In this research, titanium mesh samples coated with mixed iridium oxide-tantalum oxide layers were tested as anodes in 2 M sulfuric solution a constant current density of 0.54 A/cm2. A two-electrode cell with a bare titanium mesh serving as the cathode was used for experiments. In addition to ALTs, anodic polarization measurements were also carried out to study the changes in overpotential for oxygen evolution on electrodes before and after ALTs. Additionally, morphology and chemical composition analyses were performed on electrodes before and after ALTs using various techniques such as scanning electron microscopy (SEM) analysis, energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Chemical species that are likely to be present in the electrowinning bath were predicted using the computer software STABCAL and presented in distribution-pH and Pourbaix diagrams. The results of multiple ALTs in the absence and presence of various levels of fluoride indicate that the anode lifetime was greatly reduced by the presence of fluoride in sulfuric acid solutions. The greater the amount of fluoride added, the shorter the anode lifetime. Additionally, both in the absence and presence of fluoride, the molar ratio of IrO2 to Ta2O5 in the coating did not change during dissolution. In studying strategies to prolong the lifetime of the electrode in a fluoride-containing solution, a method of complexing fluoride ions using metallic cations such as Al3+ and Fe3+ was developed and demonstrated. The anode lifetime was successfully prolonged from 200 to over 500 hours with the addition of aluminum ions to a fluoride-containing solution. Compared with ferric ions, aluminum ions are more efficient in complexing with fluoride to extend the lifetime of electrodes.

In order to increase the current efficiency in copper electrowinning tankhouses, iron can be removed from the electrolyte using ion exchange. While this is a proven technology, very little data is available for the application of this technology to copper electrowinning electrolytes containing antimony and bismuth. The feasibility of utilizing iron ion exchange for the removal of iron from copper electrowinning electrolytes containing antimony and bismuth was studied in the laboratory. A picolylamine, a sulphonated diphosphonic, an aminophosphonic and three sulphonated monophosphonic resins were tested. The picolylamine resin was found to be completely impractical as it loaded high levels of copper. All the phosphonic resins tested loaded an appreciable amount of antimony, however, only the aminophosponic resin loaded an appreciable amount of bismuth. Tests to determine whether or not the sulphonated monophosphonic Purolite 5957 resin would continue to load antimony with time and, hence, reduce the resin's ability to remove iron gave inconclusive results. In the event that the resin's ability to remove iron is hampered due to antimony loading, testing has shown that the resin performance may be restored via a regeneration with a solution containing sulphuric acid and sodium chloride. A case study for the application of this technology to the CVRD Inco CRED plant has shown that, while iron removal by ion exchange is technically feasible, it will upset the plant's acid balance in electrolyte. Therefore, an acid removal process would need to be implemented in tandem with an iron ion exchange system. Additionally, preliminary calculations suggest that a system with a single ion exchange column may have difficulty removing sufficient iron for the CRED design conditions. Therefore, consideration should be given to the possibility of utilizing a two column system (one column loading, one column stripping). / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

Titanium production is a long and complicated process. What we often consider to be the standard method of primary titanium production (the Kroll process), involves many complex steps both before and after to make a useful product from titanium ore. Thus new methods of titanium production, especially electrochemical processes, which can utilize less-processed feedstocks have the potential to be both cheaper and less energy intensive than current titanium production processes. This project is investigating the use of lower-grade titanium ores with the electrochemical MER process for making titanium via a molten salt process. The experimental work carried out has investigated making the MER process feedstock (titanium oxycarbide) with natural titanium ores|such as rutile and ilmenite|and new ways of using the MER electrochemical reactor to \upgrade" titanium ores or the titanium oxycarbide feedstock. It is feasible to use the existing MER electrochemical reactor to both purify the titanium oxycarbide feedstock and produce titanium metal.

In order to increase the current efficiency in copper electrowinning tankhouses, iron can be removed from the electrolyte using ion exchange. While this is a proven technology, very little data is available for the application of this technology to copper electrowinning electrolytes containing antimony and bismuth. The feasibility of utilizing iron ion exchange for the removal of iron from copper electrowinning electrolytes containing antimony and bismuth was studied in the laboratory. Apicolylamine, a sulphonated diphosphonic, an aminophosphonic and three sulphonated monophosphonic resins were tested. The picolylamine resin was found to be completely impractical as it loaded high levels of copper. All the phosphonic resins tested loaded an appreciable amount of antimony, however, only the aminophosponic resin loaded an appreciable amount of bismuth. Tests to determine whether or not the sulphonated monophosphonic Purolite S957 resin would continue to load antimony with time and, hence, reduce the resin's ability to remove iron gave inconclusive results. In the event that the resin's ability to remove iron is hampered due to antimony loading, testing has shown that the resin performance may be restored via a regeneration with a solution containing sulphuric acid and sodium chloride. A case study for the application of this technology to the CVRD Inco CRED plant has shown that, while iron removal by ion exchange is technically feasible, it will upset the plant's acid balance in electrolyte. Therefore, an acid removal process would need to be implemented in tandem with an iron ion exchange system. Additionally, preliminary calculations suggest that a system with a single ion exchange column may have difficulty removing sufficient iron for the CRED design conditions. Therefore, consideration should be given to the possibility of utilizing a two column system (one column loading, one column stripping).

Thesis (MEng) -- Stellenbosch University, 2014. / ENGLISH ABSTRACT: The copper sulphate leach solutions produced during the final pressure leach stages in base metal refinery processes contain low concentrations of other precious metals (OPMs, namely Rh, Ru and Ir ) and impurities in addition to the base metals (BMs) of interest. Se and Te impurities, in particular, must be removed from the leach solution before it is fed to copper electrowinning because these species have adverse effects on electrowinning efficiency. Currently, these elements are being precipitated from the leach solution with sulphurous acid. Se precipitation is satisfactory but Te removal still proves challenging. Previous studies have shown that tellurium can either be precipitated as cuprous telluride from copper sulphate solutions by reduction with sulphurous acid alone, or by the addition of SO2 as a precipitating agent and metallic copper as an additional precipitating agent. The objective of this study was to evaluate the effects of different process variables on Te and Se recovery in order to propose operating conditions at which increased tellurium precipitation can be achieved with minimal co-precipitation of base metals of interest (notably Cu and Ni). This would also aid in the development of a better understanding of tellurium and selenium precipitation mechanisms in CuSO4-H2SO4 medium. / AFRIKKANSE OPSOMMING: Die kopersulfaat logingsoplossing wat gedurende die finale druklogingstadia in basis metaal raffinaderye produseer word bevat, behalwe vir die basis metale van belang, ook lae konsentrasies ander edelmetale (AEM, naamlik Rh, Ru, en Ir) sowel as onsuiwerhede. Se en Te onsuiwerhede, in die besonder, moet vanuit die logingsoplossing verwyder word voordat die oplossing na die koper elektrowinning gevoer word omdat hierdie spesies negatiewe effekte op die elektrowinning effektiwiteit het. Hierdie elemente word tans met swaweligsuur vanuit die logingsoplossing gepresipiteer. Se presipitasie is voldoende, maar die Te verwydering bly steeds problematies. Vorige studies het getoon dat tellurium as kuprotelluried vanuit kopersulfaat oplossings presipiteer kan word deur middel van reduksie met swaweligsuur alleen, of met die byvoeging van SO2 as presipiteermiddel en metallieke koper as addisionele presipiteermiddel. Die doelwit van hierdie studie was om die effekte van verskillende prosesveranderlikes op Te en Se presipitasie te ondersoek ten einde bedryfstoestande voor te stel wat verbeterde tellurium presipitasie toelaat met minimale kopresipitasie van basis metale van belang (hoofsaaklik Cu en Ni). Dit sal ook bydra tot die ontwikkeling van ʼn beter begrip van die tellurium en selenium presipitasie meganisme in ʼn CuSO4-H2SO4 medium.

Diante da redução dos teores de níquel em minérios sulfetados, novos estudos têm sido realizados para extração e processamento de minérios lateríticos. O processamento destes minérios gera soluções contendo cobalto, que poderia ser recuperado por extração por solventes. No entanto, esta tecnologia possui riscos com relação à saúde ocupacional e incêndios. Como possível alternativa, a eletrodiálise é uma tecnologia utilizada para recuperação de metais de fontes líquidas, permitindo a separação de cátions e ânions pela aplicação de uma corrente elétrica em dois eletrodos. Quando comparada à extração por solventes, possui menor consumo de produtos químicos, pouca geração de resíduos e operação com menor dispêndio energético. O objetivo deste trabalho foi avaliar uma rota hidrometalúrgica para recuperação de uma solução sintética de sulfatos de cobalto (II), magnésio (II), manganês (II) e cromo (III), simulando concentrações obtidas numa etapa do processamento industrial de minérios lateríticos. Para tanto, foi construída uma unidade de eletrodiálise em acrílico transparente, onde foram posicionadas as membranas de troca catiônicas e aniônicas. Nas extremidades da unidade foram posicionados eletrodos de titânio revestidos com óxido de titânio e óxido de rutênio (70TiO2/30RuO2), para o cátodo e ânodo. Tanto as membranas quanto os eletrodos possuíram área de 16 cm². Duas configurações de eletrodiálise foram estudadas, uma visando à recuperação de íons e de ácido sulfúrico, e outra visando à concentração de íons. Posteriormente, a partir da solução concentrada, foi avaliada a recuperação do cobalto por três sistemas, eletrorrecuperação, precipitação e troca iônica. A eletrorrecuperação utilizou cátodos de cobalto, alumínio e aço inoxidável, e ânodos de titânio revestido (70TiO2/30RuO2). A precipitação utilizou hidróxido de sódio e ditionito de sódio. A troca iônica foi realizada em batelada, utilizando cinco tipos de resinas. No caso do sistema com cinco compartimentos, após 64 h aplicando-se densidade de corrente de 6,25 mA.cm-², os resultados indicaram extração aproximada de 76 % para Co2+, 69 % para Mn2+, 79 % para Mg2+ e 32 % para Cr3+. A recuperação de ácido sulfúrico foi comprovada pelo aumento da concentração de H2SO4 de 0,01 para 0,1 mol.L-1 no compartimento anódico. No caso do sistema com seis compartimentos, após 136 h aplicando-se densidade de corrente de 6,64 mA.cm-², os resultados indicaram extração aproximada de 95 % para Co2+, Mn2+, Mg2+ e SO42-, e de 85 % para Cr3+. O aumento da concentração no compartimento concentrado foi de 178 % para Co2+, 145 % para Mn2+, 165 % para Mg2+ e 79 % para Cr3+. A eletrorrecuperação de cobalto foi alcançada somente com cátodo de aço inoxidável, permitindo extração de 80 % do cobalto da solução, com densidade de corrente de 14,3 a 28,6 mA.cm-2. Não foi detectada deposição de cromo. A precipitação por hidróxido não permitiu a separação do cobalto do cromo, e a precipitação do cobalto por ditionito de sódio não foi detectada. A resina M4195 teve o melhor rendimento de adsorção para o cobalto em relação ao cromo, alcançando quase 40 % de extração. Os resultados confirmaram a viabilidade da eletrodiálise para produzir soluções tratadas e soluções concentradas de íons. A troca iônica e a eletrorrecuperação tiveram os resultados mais promissores para recuperação de cobalto. Dessa forma, a rota proposta pode ser uma solução complementar para recuperação de cobalto advindo do processamento de minérios lateríticos, em relação à técnica de extração por solventes. / Due to the depletion of nickel contents in sulfide ores, new studies have been carried out to extract and process lateritic ores. The processing of these ores generates solutions containing cobalt, which could be recovered by solvent extraction. However, this technology has occupational health and fire hazards. As a possible alternative, electrodialysis is a technology used for the recovery of metals from liquid sources, allowing the separation of cations and anions by the application of an electric current in two electrodes. When compared to solvent extraction, it has lower consumption of chemicals, less generation of waste and energy operation. The objective of this work was to evaluate a hydrometallurgical route to recover a synthetic sulfate solution containing cobalt (II), magnesium (II), manganese (II) and chromium (III), simulating concentrations obtained in one step of the industrial processing of lateritic ores. For this, a transparent acrylic electrodialysis unit was constructed, with cationic and anionic ion exchange membranes. At the extremities of the unit, titanium electrodes coated with titanium oxide and ruthenium oxide (70TiO2/30RuO2), were positioned as the cathode and anode. Both the membranes and electrodes had 16 cm² of area. Two electrodialysis configurations were studied, one aiming at the recovery of ions and sulfuric acid, and the other aiming at the concentration of ions. Thereafter, from the concentrated solution, the cobalt recover was evaluated by three systems, electrowinning, precipitation and ion exchange. The electrowinning tests were performed with cobalt, aluminum and stainless steel cathodes. Titanium coated electrodes (70TiO2/30RuO2) were used as anode. In the precipitation tests, sodium hydroxide and sodium dithionite were used. The ion exchange tests were performed in batch mode, using five types of resins. For the system with five compartments, after 64 h applying a current density of 6.25 mA.cm-², the results indicated an approximate extraction of 76 % for Co2+, 69 % for Mn2+, 79 % for Mg2+ and 32 % for Cr3+. The recovery of sulfuric acid in the anode compartment was confirmed by the increase of the H2SO4 concentration from 0.01 to 0.1 mol.L-1. For the system with six compartments, after 136 h applying a current density of 6.64 mA.cm-², the results indicated an approximate extraction of 95 % for Co2+, Mn2+, Mg2+ and SO42-, and 85 % for Cr3+. The concentration increase in the concentrate compartment was 178 % for Co2+, 145 % for Mn2+, 165 % for Mg2+ and 79 % for Cr3+. The cobalt electrowinning was reached only with the stainless steel cathode, allowing an extraction of 80 % of the cobalt from the solution, with current density from 14.3 to 28.6 mA.cm-². No chromium deposition was detected. Precipitation by hydroxide did not allow the separation of cobalt from chromium, and precipitation of cobalt by sodium dithionite was not detected. The M4195 resin had the best adsorption yield for cobalt over chromium, achieving almost 40 % extraction. The results confirmed the feasibility of the electrodialysis to produce treated solutions and concentrated solutions of ions. Ionic exchange and electrowinning had the most promising results for cobalt recovery. Thus, the application of the proposed route may be a complementary solution for the recovery of cobalt from lateritic ores processing, compared to solvent extraction.

Potential new ore deposits containing significant levels of enargite, a copper arsenic sulphide mineral, are being considered for development. The processing of high arsenic copper concentrates directly in copper smelters is difficult due to environmental concerns. This thesis investigates a process using sulphation roasting as an alternative method for processing enargite concentrates; copper is recovered from the calcine by acid leaching, gold is extracted from the leach residue by conventional cyanidation and arsenic is either fixed in the calcine or precipitated from process emissions. In this research, sulphation roasting between the temperatures of 300-800oC, with varying oxygen and sulphur dioxide partial pressures, was investigated. Experiments indicated that high levels of copper extraction, as well as arsenic fixation, could be achieved from the produced calcines through hydrometallurgical processes. At operating temperatures between 400-550oC copper sulphate, copper arsenate, iron sulphate, hematite and iron arsenate form in the calcine, as well as some arsenic being volatilized as arsenic trioxide. At processing temperatures between 475-575oC, greater than 80% of the arsenic was retained in the calcine as copper and iron arsenates. Copper arsenate would be weak-acid soluble and fixed in an effluent treatment plant along with arsenic captured in the wet-gas scrubber bleed solution. As operating temperatures increase above 650oC copper sulphates were converted into oxysulphates, oxides and ferrites, hematite production was favoured, and arsenic was primarily volatilized. Increasing the sulphur dioxide addition in the reaction atmosphere resulted in additional sulphate formation and increased sulphate stability at higher temperatures. Sulphation roaster heat balances were developed for calcines produced at two temperatures, 500 and 750oC. They indicated that while high copper extraction and arsenic fixation rates could be achieved, the sulphation roasting reactions are highly exothermic and significant cooling water would need to be added. Due to these issues, it is likely that partial roasting operations would be economically favourable in greenfield operations. However, niche applications of this process in operations with existing copper SX/EW facilities in good acid markets, have the potential to be economically favourable. / Thesis (Master, Mining Engineering) -- Queen's University, 2012-08-17 20:14:36.292