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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
71

An Electrochemical and SERS Study of the Gold-Thiosulfate Interface in the Presence of Copper

Nicol, Eric 19 April 2013 (has links)
Complementary electrochemical and spectroscopic techniques were used to characterize the behavior and composition of the passive layer formed at the gold-thiosulfate interface in the presence of copper. Raman studies of three different cationic (calcium, ammonium and sodium) thiosulfate leaching solutions showed that the concentrations of sulfate, thiosulfate, trithionate and tetrathionate remained constant. Initial leaching current densities for the three systems were identical, however, significant differences were noted in the open circuit potentials of these systems. Gold nanorod electrodes were employed as substrates for Surface Enhanced Raman Spectroscopy (SERS) studies of the gold-thiosulfate interface. The composition and behavior of the passive layer at the gold- thiosulfate interface greatly differed from that of the bulk solutions. Higher order polythionate species were not observed, and significant differences were noted in the behavior of species common between the three thiosulfate leaching solutions. Passivation levels determined from SERS indicate that in the presence of copper, the cation associated with thiosulfate may play a key role in the extent of passivation on the gold surface. / Barrick Gold Corp., NSERC
72

Reciclagem de baterias de íon de Li: condicionamento físico e extração do Co. / Recycling of ion Li batteries: physical conditioning and Co extraction.

Vivian Cristina Inacio Takahashi 20 December 2007 (has links)
Com o avanço da tecnologia aplicada em aparelhos celulares, são lançados no mercado modelos menores, mais leves e com maior rapidez em seu sistema operacional. Tudo isso atrai muito os consumidores, que por sua vez, trocam seus antigos aparelhos celulares por novos e modernos. Essas adesões e trocas freqüentes de aparelhos celulares geram um descarte significativo de todos os seus componentes e dentre eles a bateria. Assim, pelo fato do cobalto estar presente nesse tipo bateria e ser um metal com alto valor agregado, ele faz parte do estudo do presente trabalho. Este trabalho tem por objetivos estudar as etapas de condicionamento físico e de lixiviação como fases iniciais do processo de reciclagem de baterias de íons de lítio. Para a caracterização das baterias, as mesmas foram desmanteladas manualmente para a separação dos componentes. Os eletrodos foram caracterizados por espectrofotometria de absorção atômica, difração de raios-X e microscopia eletrônica de varredura com analise de microrregiões. Os ensaios de lixiviação foram feitos usando-se os seguintes parâmetros: pH entre 3 e 5, temperaturas de 25 e 50ºC, relação sólido/líquido de 1/5, tempos de 1 a 4h. Foram utilizados como meio lixiviante soluções de acido sulfúrico, clorídrico e nítrico. Peróxido de hidrogênio foi adicionado ao acido sulfúrico como agente oxidante. Os resultados alcançados mostraram que entre os moinhos de martelos, de facas e de bolas o que apresentou o melhor desempenho para a moagem de baterias de íons de lítio foi o moinho de facas. O bombardeamento com ultra-som faz com que haja a liberação do material ativo dos eletrodos que fica aderido aos suportes de cobre e alumínio mesmo apos moagem. A diminuição do pH de 5 para 3 e o aumento da temperatura de 25 para 50ºC causam o aumento da velocidade de lixiviação em meio sulfúrico do oxido de cobalto. A presença de agente oxidante na lixiviação acida faz com que diminua o tempo de lixiviação do oxido de cobalto. A lixiviação com acido nítrico e com acido sulfúrico com adições de peróxido de hidrogênio são os melhores meios de lixiviação quando comparados ao acido clorídrico e ao acido sulfúrico sem oxidante para as mesmas condições de pH e de temperatura. Nas etapas de extração liquido-liquido e reextração foram utilizados os seguintes parâmetros: relação orgânico-aquoso de 1/1, temperatura de 50ºC, pH 4 e tempo de 5 minutos na etapa de extração e como solução aquosa na fase da reextração o acido sulfúrico 2M. Nas duas etapas foi utilizado como extratante o Cyanex 272 diluído em querosene. Os resultados alcançados mostraram que nos primeiros dois contatos das fases orgânicas e aquosas já se obtém as melhores porcentagens de extração e reextração. A eficiência global dos quatro contatos na etapa de extração foi de 94% e na etapa de reextracao foi de 98%. / The fast changes in technologies applied to mobile phones causes an incredible appearance of new and even better models each day. As a consequence, each year increase the amounts of waste of electronic and electric equipments including batteries that should be disposed of. The goal of the present work is to study methods of physical conditioning and acid leaching of Li-ion batteries. Hand disassembling Li-ion batteries was performed to identify and characterize the components of scrap Li-ion batteries. Materials extracted form the electrodes were characterized using X-ray diffraction, atomic absorption spectrophotometry and scanning electron microscopy coupled with EDS micro-probe. Leaching tests were carried out using the following parameters: pH (3 - 5), temperature (25 and 50ºC), solid/liquid ratio equal to 1/5, leaching time (1 to 4h). Sulfuric acid, chloridric acid and nitric acid were tested as leaching media. Hydrogen peroxide was tested as an oxidizing agent during leaching tests using sulfuric acid. The results obtained showed that knives mill presented better results to grind the scraps in comparison to hammer and balls mills. Ultrasonic treatment was effective to release the active cell materials from copper and aluminum. Decreasing pH from 5 to 3, and increasing the temperature from 25 to 50ºC cause the increasing of the leaching rate of cobalt oxide. Oxidizing conditions also increase the rate of cobalt oxide leaching. Nitric acid and sulfuric acid plus hydrogen peroxide leaching results in better leaching rates compared to chloridric acid and sulfuric acid.
73

Recuperação de metais a partir do processamento mecânico e hidrometalúrgico de placas de circuito impresso de celulares obsoletos. / Metals recovery from mechanical and hydrometalurgy processing of printed circuit boards from obsolete mobile.

Viviane Tavares de Moraes 22 December 2010 (has links)
O avanço da tecnologia de aparelhos eletro-eletrônicos favorece a troca constante dos equipamentos. O freqüente descarte de aparelhos obsoletos se torna um problema de sustentabilidade e também um problema ambiental devido ao seu acúmulo em aterros. A solução para minimizar estes impactos é a reciclagem de seus componentes. Por esta razão, o principal objetivo deste trabalho é estudar o processamento das placas de circuito impresso de telefones celulares através de operações unitárias de Tratamento de Minérios e hidrometalurgia a fim de se recuperar o cobre contido nas placas. Para isso, inicialmente, placas de circuito impresso foram processadas em moinho de martelos, a fim de liberar os materiais, em seguida foi feita a separação magnética do material cominuído. Com a fração não magnética foi feita a separação eletrostática e o material foi separado em: fração condutora, mista e não condutora, com cada fração foi feita a classificação granulométrica e, posteriormente, realizaram-se ensaios de caracterização como pirólise, digestão em água régia e análise química de espectroscopia de emissão óptica por indução de plasma. Os processos hidrometalúrgico aplicados para a recuperação de cobre nas placas de circuito impresso de aparelhos celulares obsoletos envolvem etapas lixiviação com ácido sulfúrico na ausência e na presença de peróxido de hidrogênio. Os resultados da caracterização mostraram que as placas de circuito impresso de celulares após a moagem possuem 24% de cerâmicas; 12,7% de polímeros e 63,3% de metais. Além disso, após a classificação granulométrica e a separação eletrostática os materiais não se concentraram em nenhuma fração especifica, portanto o processamento mecânico visando a recuperação de metais deve contemplar a moagem e a separação magnética. / The technology advancement of electro-electronics devices favors the constant equipment exchange. The frequent disposal of obsolete equipment becomes a sustainability problem and also an environmental problem due to their accumulation in landfills. One possible solution to minimize these impacts is the recycling of their components. For this reason the aim goal of this study is processing of printed circuit boards of mobile phones utilizing unit operation of ore treatment and hydrometallurgy to recover the copper contained in the printed. Therefore, initially printed circuit boards were processed on a hammer mill to release the materials, then it was made magnetic separation of comminuted material. With the non-magnetic fraction was made electrostatic separation in which the material was separated into: conductive, mixed and non-conductive fraction, with each fraction was made grain sized classification and then assays were performed analysis of characterize as pyrolysis, digestion in aqua regia and chemical analysis of inductively coupled plasma atomic emission spectroscopy. Hydrometallurgical processes applied to the cooper recovery in printed circuit boards of obsolete mobile phones, involve steps leaching with sulfuric acid in the absence and presence of hydrogen peroxide. The characterization results showed that the printed circuit boards of mobile phones after grinding have ceramics 24%, polymers 12.7% and metals 63.3%. Moreover, after grain sized classification and electrostatic separation the materials didn\'t concentrate in no specific fraction, therefore the mechanical processing in order to recover metals should include grinding and magnetic separation.
74

Recuperação de níquel a partir do licor de lixiviação de placas de circuito impresso de telefones celulares. / Recovery of nickel from leach liquor of printed circuit boards of mobile. Phones

Adriana Johanny Murcia Santanilla 05 December 2011 (has links)
Os resíduos de equipamentos elétricos e eletrônicos é um dos fluxos de resíduos que mais cresce no mundo. O aumento na produção destes equipamentos como resultado dos avanços tecnológicos e a sua rápida obsolescência promovem o aumento de geração deste tipo de resíduos. Portanto, este trabalho tem como objetivo estudar a recuperação de níquel presente no licor de lixiviação de placas de circuito impresso de telefones celulares obsoletos, através da aplicação de processos hidrometalúrgicos e eletrometalúrgico. Inicialmente, foram preparadas soluções sintéticas a partir da composição química do licor de lixiviação das frações magnética (MA) e não magnética (NMA) das placas de circuito impresso cominuídas. Os elementos presentes nas soluções são: ferro, zinco, níquel e alumínio. Posteriormente, foi realizada uma etapa de remoção do ferro, através de precipitação seletiva. A morfologia e a composição química do precipitado foram analisadas através de Microscopia Eletrônica de Varredura (MEV) e EDS, respectivamente. A composição química das soluções resultantes da precipitação foi determinada através da técnica de espectrofotometria de absorção atômica. Através do processo de precipitação conseguiu-se uma porcentagem de remoção de ferro na solução NMA de 99,6% e na solução MA de 99,9%, porém, observou-se também a coprecipitação de zinco, alumínio e níquel. Com as soluções resultantes desta etapa, foi realizada a purificação das soluções através de extração por solvente, utilizando Cyanex 272 como agente extratante. As variáveis estudadas nos ensaios de extração por solvente foram: pH, concentração do extratante, relação fase aquosa/orgânica (A/O) e temperatura. . Além disso, também foi determinado o número de contatos necessários para a extração de ferro, zinco e alumínio, obtendo assim, uma solução aquosa contendo unicamente níquel. Finalmente, foram realizados os ensaios de eletrodeposição para a obtenção de níquel metálico. Foi avaliado o efeito da temperatura sobre o filme depositado. A morfologia dos depósitos e a espessura da camada foram analisadas através do MEV, verificando que o aumento da temperatura influencia nas características do depósito obtido. / Electric and electronic waste (e-waste) is one of the fastest growing waste streams in the world. Continuous increasing production owing to the technological advances and the products consumption rise, all together with the rapid obsolescence of this scrap promotes the necessity of exchange and the increasing of generate waste. Therefore, the aim of this work is to study a recovering of nickel from leach liquor of cell phones printed circuit boards, through of hydrometallurgical and electrometallurgical process application. Firstly, was prepared synthetic solutions of both magnetic (MA) and nonmagnetic (NMA) fractions of printed circuit boards. The metal ions present in the synthetic solutions are: iron, zinc, nickel and aluminium. Afterwards was realized the iron removal stage, through both selective precipitation and solvent extraction process, in order to make a comparison of these techniques. The precipitates were analyzed across of scanning electron microscope (SEM), and the chemical composition of these solutions through atomic absorption spectrometry (AAS). With selective precipitation it was obtained 99,6% and 99,9% of iron removal with selective precipitation in NMA and MA solutions, respectively. Therefore, it was also observed co-precipitation of zinc, aluminium and nickel. With solutions after precipitation stage was carried out the solutions purification through solvent extraction using cyanex 272 as extractant. Solvent extraction test were studied different parameters, such as: equilibrium pH, extractant concentration, aqueous-organic (A/O) ratio and temperature. It was also determinates the stages number required for iron, zinc and aluminium extraction, to obtain nickel in aqueous solution uniquely. Finally, was carried out the electrodeposition test for obtain metallic nickel. Was analyzed the effect of temperature on the deposited layer. Surface Morphology and thickness of the deposits were evaluated by MEV, verifying that temperature increasing influences on deposited layer.
75

Mineralogical and Metallurgical Study of Supergene Ores of the Mike Cu-Au(-Zn) Deposit, Carlin Trend, Nevada

Barton, Isabel Fay, Barton, Isabel Fay January 2017 (has links)
This paper presents the results of a mineralogical and metallurgical study of supergene ores at the Mike Cu-Au(-Zn) deposit on the Carlin trend of Nevada, USA, currently held by Newmont Gold Corporation. With a metal endowment totaling >8.5 M oz. Au, 1027 M lbs. Cu, and 809 M lbs. Zn, Mike is one of the largest deposits on the Carlin trend, but it is currently uneconomic to develop. It contains an unusual and complicated suite of metals and ore minerals. This study was undertaken as a first step to investigate process options for recovering both its Cu and Au by 1) comparing the metal recoveries achieved from the supergene ores by six different lixiviants, and 2) identifying which minerals failed to dissolve in each lixiviant. The reagents selected were sulfuric, sulfurous, and methanesulfonic acids, to recover Cu, and cyanide, thiourea, and glycine, to recover Cu and Au. QEMSCAN and SEM study of six samples of different ore types and grades indicate that the Au occurs as varieties of native gold, including auricupride and electrum. Major Cu minerals are native Cu, cuprite, malachite, chrysocolla, and conichalcite (Ca-Cu arsenate), with locally significant Cu in jarosite and goethite. Gangue mineralogy is dominated by quartz, sericite, chlorite, alunite, smectite and kaolinite, K-feldspar, jarosite, and iron oxides. Bottle roll testing indicates that no single-step leaching process is likely to provide economic recovery of both Cu and Au. Sulfuric and methanesulfonic acid both recovered > 70% of the Cu except from the samples dominated by conichalcite, which was not leached effectively by any of the reagents tested. Only cyanide and thiourea recovered significant Au. Reagent consumption for cyanide, sulfuric acid, and methanesulfonic acid was generally within acceptable levels. Glycine and sulfurous acid are both uneconomic based on low recovery. Further work will focus on developing an economic process in two steps. Mineralogical study of QEMSCAN residue indicates that the non-leaching ore minerals are conichalcite and Cu-bearing Fe oxides. In addition, native Cu and cuprite do not leach well in glycine and chrysocolla does not leach well in thiourea or cyanide. Other observed mineralogical changes include the total loss of dolomite and partial loss of alunite and iron oxide from all samples, with apparent gains in jarosite.
76

Application of bidentate N,N'-donor extractants in the hydrometallurgical separation of base metals from an acidic sulfate medium / Application of bidentate N,N'-donor extractants in the hydrometallurgical separation of base metals from an acidic sulphate medium

Okewole, Adeleye Ishola January 2013 (has links)
Bidentate imidazole-based extractants, 1-octylimidazole-2-aldoxime (OIMOX) and 1-octyl-2-(2′-pyridyl)imidazole (OPIM), along with dinonylnaphthalene sulfonic acid (DNNSA) as a synergist, were investigated as potential selective extractants for Cu²⁺and Ni²⁺ respectively from base metals in a solvent extraction system. The study was extended to evaluate the sorption and separation of Ni²⁺ from other base metals in a solid-solution system using microspherical Merrifield resins and nanofibers functionalized with 2,2′-pyridylimidazole. Copper was effectively separated with OIMOX and DNNSA as extractants from nickel with ΔpH½ ≈1.05 and the extraction order of Cu²⁺ > Ni²⁺ > Zn²⁺ > Cd²⁺> Co²⁺ was achieved as a function of pH. At pH 1.65 the extracted copper, from a synthetic mixture of the base metals reached 90.13(±0.90)%, and through a two-step extraction process 98.22(±0.29)% copper was recovered with negligible nickel and cobalt impurities. Stripping of the copper from the loaded organic phase using TraceSelect sulphuric acid at pH 0.35 yielded 96.60(±0.44)% of the loaded quantity after the second stage of stripping. The separation of Ni²⁺ from the borderline and hard acids; Co²⁺, Cu²⁺, Zn²⁺, Fe2²⁺, Fe²⁺, Mn²⁺, Mg2²⁺ and Ca²⁺ at a pH range of 0.5-3.5 with OPIM and DNNSA was acvieved to the tune of a ΔpH½≈ 1.6 with respect to cobalt from a sulfate and sulfate/chloride media. A three-stage counter-current extraction of Ni²⁺, at the optimized pH of 1.89, from a synthetic mixture of Ni²⁺, Co²⁺ and Cu²⁺, yielded 99.01(±1.79)%. The total co-extracted Cu²⁺ was 48.72(±0.24)% of the original quantity in the mixture, and it was 19.85(±0.28%) for Co²⁺. The co-extracted Cu²⁺ was scrubbed off from the loaded organic phase at pH≈8.5 by using an ammonium buffer, while co-extracted Co²⁺ was selectively and quantitatively stripped with H₂SO₄ at pH 1.64. The total recovery of Ni²⁺ by stripping at pH 0.32 was 94.05(±1.70)%. In the solid-liquid system, Ni²⁺ was separated from Co²⁺, Cu²⁺, and Fe²⁺ with the microspherical resins funtionalised with 2,2′-pyridylimidazole by a separation factor (β) in the range 22-45. Electrospun nanofibers as sorbents yielded high sorption capacity in the range of 0.97 - 1.45 mmol.g⁻¹ for the same metals ions. Thus, 1-octylimidazole-2-aldoxime (OIMOX), and1-octyl-2-(2′-pyridyl)imidazole (OPIM) can be effectively utilized alongside DNNSA as a co-extractant in the separation of Cu²⁺ and Ni²⁺ respectively from base metals in acidic sulfate medium in a solvent extraction process, and the latter as a selective ligand in the solid-liquid separation of Ni²⁺ from Co²⁺, Cu²⁺, and Fe²⁺.
77

Zinc recovery from baghouse dust generated at Ferrochrome foundries

Strobos, Johannes Gerhardus 31 October 2005 (has links)
During the production of ferrochrome in electric arc furnaces, a dust is captured in baghouse filters as a means of air pollution control. This dust contains various metals such as chromium, zinc, iron, aluminium and magnesium. Due to the presence of hexavalent chromium in the dust, which is both toxic and carcinogenic, it requires disposal at a hazardous waste disposal site, entailing high cost. The possibility exists that these costs could be reduced if metals such as zinc can be recovered from the dust through, inter alia, leaching. Experiments were performed to determine suitable conditions for the leaching of zinc from such a baghouse dust. A two step leaching procedure was followed which prevented the formation of silica gel. The most favourable conditions for zinc extraction was with a sulphuric acid concentration of 336 g/l and an acid to dust ratio of 0,56. Under these conditions zinc was selectively leached with regard to iron and aluminium. The percentage recovery for zinc was 71,2%, aluminium 1,8% and iron 0,1%. It was concluded that the second step (dilution) of leaching did not have a significant influence on the percentage extraction of metals from the dust. Consideration of the chemical treatment cost of waste streams produced led to the conclusion that zinc recovery from baghouse dust is not an economically feasible project viewed in isolation. However, compared to disposal at a hazardous waste disposal site such as Holfontein, approximately R467 054,00 per annum (based on a seven day week and baghouse dust production of 3 600 kg/day) can be saved. / Dissertation (MEng (Environmental Engineering))--University of Pretoria, 2006. / Chemical Engineering / unrestricted
78

Exploring the Reductive Pathway for the Hydrometallurgical Production of Copper from Chalcopyrite

Vardner, Jonathan Thomas January 2021 (has links)
The high demand for copper is coinciding with a sharp decline in the grade of copper reserves, and as a result, copper scarcities are expected to arise in the coming decades. In this work, a transformative hydrometallurgical process is being developed to lower the costs of copper production and thereby sustain the use of copper throughout the global transition to renewable energy technologies. The focal point of the hydrometallurgical process is the reductive treatment of chalcopyrite, which is in contrast to the oxidative treatment more commonly pursued in the literature. Chalcopyrite may be reduced directly by the cathode of an electrochemical reactor, which is monitored by atomic absorption spectroscopy (AAS), x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS). The efficiency of the electrochemical reaction is optimized by adjusting the electrode materials, applied current density, and reactor design. Chalcopyrite may also be reduced by reaction with the vanadium (II) ion, which circumvents engineering challenges associated with slurry electrodes but requires the separation and electrochemical regeneration of the vanadium (II) ion. A preliminary technoeconomic analysis suggests that both reduction pathways may be competitive with the pyrometallurgical standard for copper production. The performance of vanadium redox flow batteries (VRFBs) is hindered by the diffusion and migration of the vanadium species across the separator, however the migration of vanadium species has not been accurately measured or characterized with values of the transference numbers. In this work, models based on dilute solution theory and concentrated solution theory are developed to introduce the dimensionless ratio of migration to diffusion (M/D) to the literature. It is shown that transference numbers may be measured with high accuracy and precision for experiments conducted in the migration-dominated regime. An experimental procedure is designed to measure vanadium crossover as a function of current density for vanadium-containing electrolytes of various state of charge (SOC), state of discharge (SOD), and sulfuric acid concentration. Model-guided design of experiment is used to estimate the transference number of the vanadium species in Nafion 117 with minimal uncertainty related to unknown or unmeasured physical properties. Markov Chain Monte Carlo simulations are used to quantify the relative uncertainties of the transference number estimates to be less than five percent, consistently. The transference number estimates are related to faradaic efficiency loss and capacity fade of working VRFBs operating in the migration-dominated regime. The technique used in this work may be generalized to measure salt transference numbers in novel electrochemical systems and membrane separators to inform their rational design.
79

THERMODYNAMIC MODELING AND EQUILIBRIUM SYSTEM DESIGN OF A SOLVENT EXTRACTION PROCESS FOR DILUTE RARE EARTH SOLUTIONS

Chandra, Alind 01 January 2019 (has links)
Rare earth elements (REEs) are a group of 15 elements in the lanthanide series along with scandium and yttrium. They are often grouped together because of their similar chemical properties. As a result of their increased application in advanced technologies and electronics including electric vehicles, the demand of REEs and other critical elements has increased in recent decades and is expected to significantly grow over the next decade. As the majority of REEs are produced and utilized within the manufacturing industry in China, concerns over future supplies to support national defense technologies and associated manufacturing industries has generated interest in the recovery of REEs from alternate sources such as coal and recycling. A solvent extraction (SX) process and circuit was developed to concentrate REEs from dilute pregnant leach solutions containing low concentrations of REEs and high concentrations of contaminant ions. The separation processes used for concentrating REEs from leachates generated by conventional sources are not directly applicable to the PLS generated from coal-based sources due to their substantially different composition. Parametric effects associated with the SX process were evaluated and optimized using a model test solution produced based on the composition of typical pregnant leach solution (PLS) generated from the leaching of pre-combustion, bituminous coal-based sources. Di-2(ethylhexyl) phosphoric acid (DEHPA) was used as the extractant to selectively transfer the REEs in the PLS from the aqueous phase to the organic phase. The tests performed on the model PLS found that reduction of Fe3+ to Fe2+ prior to introduction to the SX process provided a four-fold improvement in the rejection of iron during the first loading stage in the SX circuit. The performances on the model system confirmed that the SX process was capable of recovering and concentrating the REEs from a dilute PLS source. Subsequently, the process and optimized parametric values were tested on a continuous basis in a pilot-scale facility using PLS generated from coal coarse refuse. The continuous SX system was comprised of a train of 10 conventional mixer settlers having a volume of 10 liters each. A rare earth oxide (REO) concentrate containing 94.5% by weight REO was generated using a two- stage (rougher and cleaner) solvent extraction process followed by oxalic acid precipitation. The laboratory evaluations using the model PLS revealed issues associated with a third phase formation. Tributyl Phosphate (TBP) is commonly used as a phase modifier in the organic phase to improve the phase separation characteristics and prevent the formation of a third phase. The current study found that the addition of TBP affected the equilibrium extraction behavior of REE as well as the contaminant elements., The effect on each metal was found to be different which resulted in a significant impact on the separation efficiency achieved between individual REEs as well as for REEs and the contaminant elements. The effect of TBP was studied using concentrations of 1% and 2% by volume in the organic phase. A Fourier Transform Infrared (FTIR) analysis on the mixture of TBP and DEHPA and experimental data quantifying the change in the extraction equilibrium for each element provided insight into their interaction and an explanation for the change in the extraction behavior of each metal. The characteristic peak of P-O-C from 1033 cm-1 in pure DEHPA to 1049 cm-1 in the 5%DEHPA-1%TBP mixture which indicated that the bond P-O got shorter suggesting that the addition of TBP resulted in the breaking of the dimeric structure of the DEHPA and formation of a TBP-DEHPA associated molecule with hydrogen bonding. The experimental work leading to a novel SX circuit to treat dilute PLS sources was primarily focused on the separation of REEs from contaminant elements to produce a high purity rare earth oxide mix product. The next step in the process was the production of individual REE concentrates. To identify the conditions needed to achieve this objective, a thermodynamic model was developed for the prediction of distribution coefficients associated with each lanthanide using a cation exchange extractant. The model utilized the initial conditions of the system to estimate the lanthanide complexation and the non-idealities in both aqueous and organic phases to calculate the distribution coefficients. The non-ideality associated with the ions in the aqueous phase was estimated using the Bromley activity coefficient model, whereas the non-ideality in the organic phase was computed as the ratio of the activity coefficient of the extractant molecule and the metal extractant molecule in the organic phase which was calculated as a function of the dimeric concentration of the free extractant in the organic phase. To validate the model, distribution coefficients were predicted and experimentally determined for a lanthanum chloride solution using DEHPA as the extractant. The correlation coefficient defining the agreement of the model predictions with the experimental data was 0.996, which is validated the accuracy of the model. As such, the developed model can be used to design solvent extraction processes for the separation of individual metals without having to generate a large amount of experimental data for distribution coefficients under different conditions.
80

A fundamental study of the dissolution of gold from refractory ores

Lorenzen, Leon 12 1900 (has links)
Thesis (PhD)--Stellenbosch University, 1992. / ENGLISH ABSTRACT: The dissolution of gold from refractory ores is a complex kinetic problem involving a number of chemical, mass transport and mineralogical factors. In most Witwatersrand ores in South Africa more than 97 % of the gold is dissolved in cyanide medium after a residence time of about 16 hours in pachuca tanks. This high percentage may be the reason why so little fundamental research has been done into the mechanism and kinetics of the leaching process. With the increasingly lower grades of ore mined, the introduction of backfill mining, and the reduction of profit margins, it has become imperative to increase the efficiency of gold dissolution. The effects of the chemistry and particle size on the dissolution of gold in each sample of ore were studied in detail. The emphasis in this study is on the effect of the leaching behaviour of various ore constituents on the rate of gold dissolution. Interferences with the leaching of gold in contact with other minerals or metals could be attributed to the galvanic interaction (electrical conductivity) between the gold and the mineral and to the formation of a surface film on the gold surface. Sulphide minerals and their oxidation products cause the largest decrease in gold dissolution rate. Galena enhances the rate of gold dissolution owing to dissolved Pb(II)-ions. Gold in contact with conductive minerals passivates as a result of the enhanced magnitude of the cathodic cu1Tent. In all experiments the rotating disc of gold passivated so that the rate of dissolution was much slower than that predicted by a mass-transport limiting model. The various films that form on the surface of the gold and associated minerals, as well as the galvanic interaction, depend largely on the pretreatment of the ore. Pre-elimination of host minerals from the gold bearing ore increases the dissolution rate of gold, and explains the kinetics of reaction on the gold surface to a large extent. The selective destruction of the various minerals with oxidative acid leaches destroys and/or decomposes certain minerals which may form films on the gold surface by precipitation. The chemical composition of these films and precipitates depends on the mineralogy of the sample. These films may be oxides, sulphides, carbonates and cyanide complexes. The complexes can be destroyed, depending on the nature of the film, by interstage dilute acid and/or cyanide washes in an agitated vessel. The destruction of the films exposes the gold surface for cyanidation. A simple distribution function similar to the King liberation model is proposed and tested to describe the dissolution step in the multi-step leaching mechanism. For the King model, good agreement is shown with experimental results. For the liberation results obtained by leaching in this study, the trend is co1Tect, but calibration is required for a close fit. A potentially important use for the liberation model by leaching is to predict the leachable or free gold in an ore from the free gold in the complete sample. This approach for studying the leaching behaviour of different gold bearing minerals has provided reasons why some ores leach better than others. / AFRIKAANSE OPSOMMING: Die loging van goud vanuit weerbarstige ertse is 'n komplekse kinetiese probleem wat verskeie faktore soos massa-oordrag, chemiese aspekte en mineralogiese ingeweefdheid insluit. Goud ekstraksies so hoog as 97 % in sianied oplossings in Pachuca reaktore na ongeveer 16 uur logingstyd word behaal in die meeste Witwatersrand ertse in Suid-Afrika. Hierdie hoë ekstraksies mag dalk die rede wees vir die min fundamentele navorsing oor die ekstraksie van goud vanuit minerale in 'n spesifieke erts. Die dalende erts grade, die verlaging van winsgrense en die terugplaas van geloogde erts in die myn noodsaak verbeterde goud ekstraksie. Verkeie faktore nl., chemie, diffusie, partikelgrootte en oplosbaarheid van goud in elke monster erts is in hierdie studie ondersoek. Die sentrale tema was om die logingsgedrag van goud vanuit verskeie minerale in 'n erts te bepaal. Galvaniese interaksie (hou verband met elektriese geleidingsvermoeë) en film vorming is die belangrikste faktore wat die loging van goud in kontak met minerale nadelig beïnvloed. Sulfied minerale en hul oksidasie produkte speel die grootste rol in die verlaging van die tempo van goudloging. Galena verhoog die tempo van goudloging as gevolg van die Pb (II)- ione in oplossing. Goud in kontak met geleidende minerale passiveer as gevolg van die verhoogde katodiese stroomdigtheid. In alle eksperimente met die roterende skyf (goudskyf) apparaat, passiveer die goudskyf in so 'n mate dat die logingstempo baie stadiger is as wat voorspel word met die massa-oordrags model. Die onderskeie films wat vorm op die goud- en geassosieerde minerale se oppervlaktes, asook die galvaniese interaksies, is 'n funksie van die voorafbehandeling van die erts. Die selektiewe eliminering van minerale vanuit 'n gouddraende erts verhoog die tempo van goudloging drasties en dit beskryf die kinetika van goudloging op die goudoppervlak in 'n groot mate. Die selektiewe eliminering van minerale deur gebruik te maak van oksiderende suurlogings, vernietig sekere van die minerale wat films op die goudoppervlakte kan veroorsaak deur middel van presipitasie. Die chemiese samestelling van hierdie films hang af van die mineralogie van die monster. Dit bestaan meestal uit oksiedes, sulfiedes, karbonate en sianiedkomplekse en hulle kan vernietig word deur middel van inter-stadia verdunde suur-en/of sianied wasse. 'n Eenvoudige distribusiefunksie, soortgelyk aan die King bevrydingsmodel word voorgestel en eksperimenteel getoets om die logingstap in die multi-stadia logingsmeganisme te beskryf. Vir bevryding deur loging, is die neiging van King se model korrek, maar kalibrasie word benodig vir goeie passing. 'n Potensiele gebruik van die aangepaste model is om vrye of loogbare goud in 'n spesi fieke partikel grootte fraksie van 'n erts te voorspel as die vry goud in die totale fraksie bekend is. Die resultate uit hierdie studie kan gebruik word om die logingsgedrag van gouddraende minerale te voorspel en te beskryf, en dus veduidelik hoekom goud uit sekere ertse beter loog as uit ander.

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