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By Jeffrey Shepherd, Scott R. Smith, Eduard Guerra

"Electrochemical and spectroscopic evidence for the dissolution of a Au electrode by meso-2,3- dimercaptosuccinic acid (DMSA) from an acidic LiCl04 electrolyte is presented. Near the potential of zero charge, DMSA was determined to form a stable layer on the metal surface but at more anodic polarizations, DMSA was displaced from the metal through an oxidative process. The anodic displacement of the layer from the electrode resulted in a small amount of Au that was detected in the electrolyte using atomic absorption analysis. The extent of Au dissolution, was monitored while holding the potential of the electrode for 24 hours at the thermodynamic Eo/H,O in LiCl04 electrolytes containing 10 mM DMSA. This routine resulted in detectable quantities of a soluble Au-DMSA complex in the electrolyte and the greatest leaching was observed at a pH = 2.0. At room temperature, the leaching rate was stable at 10.9 µg cm·2 hr·' however, upon increasing the temperature to 50.0°C, the rate of Au dissolution increased yielding an average rate of extraction of 40.1 µg cm·2 hr- 1. Interestingly, after the first 12 hours of leaching at 50.0°C, the leaching current decreased dramatically suggesting surface passivation which prevented further Au extraction. The implications of this process in the industrial leaching of Au will be discussed.IntroductionThe use of cyanide in the industrial process of leaching Au from ores has raised concerns regarding both operational safety and environmental issues surrounding the disposal of spent leaching eftluents in tailings ponds. Depending on the chemical nature of the processed ore, the spent solutions that are released into the tailings ponds can contain toxic cyanide, either dissolved or complexed with different metals and may pose serious risk to wildlife as well as freshwater contamination to nearby water systems. Because of these issues, some recent studies have focused on the exploration of more environmentally-friendly molecules to selectively leach Au with appropriate kinetics. However, to effectively leach Au into an aqueous solution, a suitable ligand that reacts to form a stable chemical bond with Au is needed to form soluble Au complexes that can be later recovered [I]. Recently several sulfur bearing alternatives have been shown to leach significant quantities of Au in aqueous solutions. These include thiourea [2], thiocyanate [3], and thiosulphate [4]. However, alkylthiols are also known to quickly form a stable covalent Au-S bond [5], but have been relatively understudied in term of their ability to leach Au in solution, even though some short chain thiols are water soluble and relatively nontoxic."

Jan 1, 2012

By Hongmin Zhu, Qiuyu Wang, Shuqiang Jiao, Guojing Hu

"The equilibrium between titanium ions and metal titanium was investigated in fluoride-chloride molten salt. The electrochemical properties of titanium ions in fluoride-chloride were studied on a molybdenum electrode by cyclic voltammetry (CV) and square wave voltammetry (SWV). The equilibrium constant of the equilibrium between titanium ions and metal Ti was calculated in KCI-NaCl- 2.5wt %K2 Tif 6 at the temperature of 1073K.IntroductionTitanium, the ninth most abundant element in the earth's crust, is endowed with high strength, low density, excellent flexibility, strong spring back characteristics, high-temperature performance, corrosion resistance and biocompatibility. These characteristics make titanium eminently suitable to be used in aerospace, marine industries, and harsh chemical environments. Although it has many excellent properties, the application of titanium in industry was limited by its high-cost. Therefore, many methods have been investigated for producing high-purity titanium at low cost. Electrolysis, involving the extraction and preparation of pure metal from ore using an electrolytic process, is considered a promising method for titanium metallurgy. Many studies have focused on the electrochemical behaviour and electrodeposition of titanium in molten chloride, fluoride, and chloride-fluoride electrolytes (1-IOJ. The electroreduction mechanism of Ti3+ ions in molten alkali chlorides has previously been studied by several workers. Two reduction steps, Ti3+ -Ti2+ -Ti, have been observed in various molten alkali chlorides [IJ. One reduction step, Ti3+ -Ti, has been observed in alkali fluoride molten salts l21. The behaviour of Ti4+ in fluoride or chloride-fluoride molten salts has also been investigated in the literature; it was proposed that the reduction of Ti4+ ions in the molten salts proceeded in a two step process: Ti4+-Ti3+-Ti l3l or a three step process: Ti4+ -Ti3+ -Ti2+-Ti ri. 4l Indeed, the stability of the titanium oxidation states depends on the bath composition l5l. The valence state was Ti2+ in alkali chloride melts, which was a lower oxidation state and correspondingly, in alkali fluoride melts, the higher oxidation states ofTi4+ and Til+ were more stable.The aim of the present work is to explore the effect of F/Cl atomic ratio on the equilibrium between titanium ions and metal titanium in fluoride-chloride at the temperature of 1073K. The electrochemical properties of titanium ions in fluoride-chloride were studied on a molybdenum electrode by cyclic voltammetry (CV) and square wave voltammetry (SWV). The solubility product of the equilibrium between titanium ions and metal Ti was calculated."

Jan 1, 2012

By Yang Tian-zu

Sodium pyroantimonate which is widely used as the clarifier in the glass industry and as the synergist in anti-flaming industry respectively has a production history of about 30 years in China. At present there is the production capacity of about 20,000 tons per year in China and China is chief producer of sodium pyroantimonate. In this work the production processes adopted by the producers of China, the operation conditions and the product qualities of sodium pyroantimonate prepared by different preparation methods have been summarized, and on the basis of comparing the advantages and disadvantages for each process the most advanced method - the air-oxidation method was introduced in detail. The production processes of sodium pyroantimonate mainly include the method of oxidation by sodium nitrate, the oxidation method of hydrogen peroxide, the potash salt method, the chlorination method and the air-oxidation method etc. The method of oxidation by sodium nitrate in which the crude antimony oxide, sodium carbonate and sodium nitrate are separately used as the raw material, the flux agent and the oxidant, has the advantage of short and simple technological process, but low grade quality of sodium pyroantimonate and bringing about serious environmental pollution are the disadvantages and this method has been substituted by other methods. Sodium pyroantimonate can be directly prepared by the hydrogen peroxide oxidation method with the advantages of simple technological process, high grade quality of the product and little environmental pollution. High grade quality of sodium pyroantimonate can be also synthesized by the potash salt method, in which industrial antimony white, the hydrogen peroxide, potassium hydroxide and sodium hydroxide are applied as the starting material. The disadvantages of these two preparation methods are high production cost and high requirements on the raw materials. The chlorination method with the crude antimony oxide, hydrochloric acid and chlorine as the raw material has the advantages of low production cost and high grade quality of the product. However complex process, high requirement of anti-corrosion for the equipments and producing plenty of waste water limit its application. The air-oxidation method with stibnite/jamesonite concentrate, sodium sulfide, and sodium hydroxide as the raw material and atmosphere as the oxidant is a newly developed method and its advantages are low production cost and the complex raw material can be treated by this method and its disadvantage is that the quality of sodium pyroantimonate is lower than that prepared by the oxidation method of hydrogen peroxide and the potash salt method.

Jan 1, 2006

By David N. Hanlon

The effect of high-temperature plastic deformation of the austenitic phase (y) on the subsequent phase transformation to ferrite (a) has been experimentally investigated, and modelled using a physically-based model. The effect is of importance for steel sheet, in view of me significance of the phase transformation with respect to the eventual properties of the material. In this paper the kinetics of the y ? a phase transformation has been studied after different degrees of prior deformation. The degree of deformation is varied by applying different deformation temperatures and strain rates, and by allowing a varying extent of recovery and recrystallisation. Consequently, both dynamic and static recovery and recrystallisation have been involved. The dilatometric observations on the phase transformation have been modelled using an interface-mobility model, in which the effect of the dislocation structure is introduced as an additional driving-force term. The effect of the stored energy on the nucleation process, which appears to be affected more strongly than the growth of ferrite, is examined in terms of the classical nucleation theory.

Jan 1, 2001

By S. P. Jupp

A 2-D coupled thermo-mechanical model was developed to simulate hot tandem rolling of AA5056 aluminum alloy using the commercial finite element software package, ABAQUS The model was used to predict the temperature, strain rate and strain distribution in the strip at any position in the roll bite and was verified through comparisons with literature results in terms of both temperature and strain predictions at the roll bite exit. A sensitivity analysis indicated that model predictions of temperature and strain at the roll bite exit were sensitive to the friction coefficient and moderately sensitive to the heat transfer coefficient for the conditions studied. Microstructure equations taken from the literature were used to make predictions at various positions in the strip. The temperature, strain rate and strain vary dramatically through the thickness of the strip in the roll bite. The sensitivity of the microstructure predictions to these parameters was assessed and it was found that using average values of temperature and strain rate in the roll bite versus exit values significantly influenced the resulting microstructure predictions.

Jan 1, 2001

By P. M. Swash

The determination of the heavy minerals in beach sand samples is highly dependent on the preparation technique used. In this paper a simple reproducible method for the quantification of "recoverable" ilmenite, zircon, rutile and leucoxene by magnetic separation, is described. The procedure recommended yields information relevant to the metallurgical processing of the ore rather than to the total heavy minerals present in the samples. Finally the determination of mineral reserve estimations and grade assessments is greatly facilitated when this "mineral assay" method is employed. An assortment of other mineralogical methods are described including SEM, EMPA, XRD, XRF, Image analysis, Mossbauer. clerici and perm roll separations. The methods are briefly examined and the practical information that can be gained by using such techniques are reviewed. Experience has shown that an understanding of the relationship between the physical and chemical properties of the heavy minerals can contribute to the prediction of mineral particle behaviour. Such information may ultimately help reduce the prospect evaluation period and minimise expenditure on metallurgical testwork.

Jan 1, 1991

By Yong Kuk Park

The horizontal cold chamber die casting process can produce a wide range of near-net shape, non-ferrous castings with small dimensional variation, excellent surface finish and very complex geometries. However, top quality die castings can be achieved only when optimal performance of the cold chamber and plunger is maintained during the molten metal injection phase of the process. Cold chambers (shot sleeves) are known to deteriorate fast and sometimes fail catastrophically because of poor design. Catastrophic fracture and wear due to deformation are leading causes to degrade quality, increase downtime and thereby decrease productivity and profitability. Therefore, a systematic approach to minimize irregular and adverse conditions which prevent an intended injection profile, is highly desirable. To eliminate them, design criteria for shot sleeves were developed using analytical tools and available experimental data. The correlation between design and mechanical failures of shot sleeves was shown by the data obtained from the die casting industry. Also, the relationship between die casting process parameters and deterioration/ failure mechanisms were carefully evaluated.

Jan 1, 1996

By Zhijing Zhang

Long-term thermal stability of ionic liquids is essential for reliable performance of ionic liquids in any engineering applications. TGA studies were carried out on a series of ionic liquids with different cations and anions such as 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), 1-hexyl-3-methylimidazolium chloride ([C6mim]Cl), 1-hexyl-3¬methylimidazolium tetrafluoborate ([C6mim]BF4), 1-hexyl-3-methylimidazolium hexafluorophosphate ([C6mim]PF6), 1-octyl-3-methylimidazolium hexafluorophosphate ([Csmim]PF6), and 1-butyl-3-methylimidazolium bis(trifluromethanesulflonyl)imide ([C4mim][Tf2N]). The short-term thermal stability of ionic liquids was evaluated by measuring the onset temperature of decomposition of ionic liquids, and the long-term thermal stability of ionic liquids was also evaluated by weight loss of ionic liquids over a long period of time at various temperatures. The experimental results showed that the long-term thermal stability of ionic liquids decreased with increasing temperature and was significantly lower than the onset temperature of decomposition of ionic liquids.

Jan 1, 2002

By W. D. Cho

Fast dissolution of nonmetallic inclusions such as alumina particles in molten slags has been required in secondary steelmaking -ladle and tundish - to minimize the amount and the size of nonmetallic inclusions in steel products. In the present work, the dissolution behavior of alumina particles in molten CaO-A12O3 and CaO-A12O3-SiO2 slags at the temperatures between 1450 and 1550°C have been investigated in terms of kinetics and mechanism. Alumina particles were added directly into the slags and the variation of the particle size with time was determined using optical and electron microscopies. The conventional types of slag for ladle and tundish were included in the dissolution study. The effects of Al2O3, Siq, CaF2 and MgO contents on the dissolution rate of alumina particles have also been determined. The diffusion boundary layer between alumina particle and bulk slag phase has been observed and analyzed using SEM and EDS. Based on the analysis of kinetic data and the boundary layer, the dissolution mechanism has been discussed.

Jan 1, 2002

By Ramana G. Reddy

In the past, many lead-containing slags and wastes were stored in piles or landfills. However, shortages of landfill space as well as increased public, concern about the toxic nature of disposing lead containing industrial wastes in landfills have led to review of disposal methods. Several lead wastes are processed to provide commercial products. They are used on-site in land reclamation projects. or are processed and sold as a by-product. These by-products contain nutrient elements needed for plants or animals and also may contain heavy? metal contaminants such as As, Cr. Cu, Zn and Ph. Use of such by-products containing unacceptable levels of these contaminants could cause plant and animal toxicity. In this paper. role of viscosity in conversion of lead slag wastes into commercial products containing ,low content of lead and other, heavy metals is presented. Effects of slag viscosity on the velocity of movement of metal' and matte prills through themolten slag layer in the melting furnace is discussed. Current and emerging slag cleaning technology, foamed, granulated and pelletized slag technologies are reviewed.

Jan 1, 1995

By John Frederick Colloghon, O&apos

Bulong remains the only hydrometallurgical process plant in the world that recovers nickel and cobalt directly from high pressure acid leach (HPAL) laterite leach liquors without need for precipitation of an intermediate product (e.g. sulphide, hydroxide or carbonate). Direct solvent extraction (DSX) of both nickel and cobalt in combination with electrowinning of nickel has been operation at Bulong since early 1999. Focus in the first years has been on ramp-up and resolution of commissioning problems. More recently the focus has been on de-bottlenecking and process optimisation. A number of significant process problems have been resolved, the most difficult being the formation of gypsum in the nickel solvent extraction circuit. Sound control of process chemistry is essential to ensure the production of high quality nickel and cobalt products at the lowest possible cost. This paper describes the numerous changes and enhancements to the process chemistry and plant equipment at Bulong and discusses the importance of ore leach chemistry on downstream impurity metal removal. Potential additional enhancements to further reduce unit costs are also presented.

Jan 1, 2004

By G. Riverin, C. Simard, W. D. Stevens

"An on-line technique to measure the efficiency of decoating I delacquering processes is being developed by Alcan' s Arvida R & D Centre. Decoating processes are used to remove moisture and coatings from shredded coated material such as Used Beverage Containers (UBC) before melting. Complete removal has been demonstrated to maximize metal recovery. Quantifying the weight of carbon and organic residue adhering to the shred surfaces is very difficult to measure directly, as the material can be highly folded. The technique developed indirectly measures the residue remaining by analysing the concentration of CO evolved in the decoater end zone exhaust gas.A commercial CEMS (Continuous Emission Monitoring System) incorporating an infrared type CO gas analyser was modified for on-line process exhaust gas analysis. Both pilot and plant trials had demonstrated that the CO concentration measured was inversely proportional to the efficiency of the organic removal achieved. As the quality of coated purchased scrap can be highly variable in moisture and organic content, continuous measurement should permit adjusting the feed rate and other decoater process parameters to the quality of decoating required."

Jan 1, 2000

By Larry Southwick

In the early 1940's, the Caron ammonia ? ammonia carbonate leach process was used to produce nickel from Mayari ores at the Nicaro plant in Oriente Province, Cuba. While plant operation was generally successful, it was not broadly economical and was shut down. The plant was later restarted in the 1950's and a number of investigations initiated to resolve the more serious operational and performance issues. Processing steps studied included iron reduction (chemistry ? nickel and iron, reductant, equipment), ore variability (homogeneity and consistency of mineral concentrations, serpentine vs. laterite), leach solution strength, nickel recovery (temperature ? reduction and leaching, reoxidation) and a variety of other topics. These studies and their findings will be discussed. Caron himself obtained good results on these ores in the laboratory. They could not be duplicated in the field, the reasons for which will be reviewed. (Note: the ore looked like garden dirt; charcoal made from palm trees was one of the reductants attempted; and ammonia was the leach solution. Mixing the three, so to speak, was to yield nickel.)

Jan 1, 2006

By S. C. Grand, T. J. Auping, K. Born

Process control, environmental monitoring, budgeting and accounting are based on process data. Without appropriate tools for data analysis, the process data could remain unused and wasted. This paper demonstrates how data reconciliation can be used as a tool to develop closed mass balances. Mass balances are the initial step in plant optimisation (technical, economical or environmental). From mass balances, fundamental process models can be developed. These balances link process parameters (e.g., feed materials) to process performance (e.g., recovery of valuable elements). Some of these models could find their way into simulators useful to plant operators. Classical regression methods regularly fail when they are applied to complex non-linear problems involving a large number of variables. Alternatively, multiparametrical regression analysis can be successfully applied with the aid of neural networks based on reconciled data. Both methods have been applied to plant data originating from the hydrometallurgical zinc plant at Ruhr-Zink, which in this paper serves as a case study. Very promising and useful results were obtained from this study.

Jan 1, 2000

By Michael J. Nicol

One of the preferred methods for the recovery of gold from refractory gold ores and concentrates involves pressure oxidation in acidic solutions. The main refractory gold-containing minerals are pyrite and arsenopyrite and there is evidence that the presence of even small amounts of chloride can inhibit the oxidation of these minerals and also substantially reduce the recovery of gold. In this paper, the results of a study of the anodic (oxidation) and cathodic (reduction) behaviour of pyrite electrodes in acidic sulfate solutions containing ferric ions at different chloride concentrations and temperatures up to 200oC and pressures of 2000KPa are presented. The electrochemical studies have been complemented by pressure oxidation experiments on a refractory gold concentrate. Results have shown that, as the chloride concentration increases, the anodic reactivity of pyrite is largely unaffected but the rate of the cathodic reduction of iron(III) decreases. The rate of oxidation of a sulfide concentrate and the recovery of gold by cyanidation of the residues decreases at high concentrations of chloride.

Jan 1, 2003

By Y. F. Jia

Arsenic constitutes a major contaminant for the hydrometallurgical industry. Its removal and immobilization from process effluents typically involves lime neutralization and co-precipitation with ferric iron (Fe (III)/As(V)>3). Alternatively, precipitation of scorodite (FeAsO4?2H2O (cr)) may be applied to arsenic fixation. The mechanism of arsenic fixation in the former process has been suggested to be surface adsorption. Unequivocal characterization of these products is difficult because of their amorphous nature hence a variety of methods need to be applied including the particularly powerful method, extended x-ray absorption fine structure (EXAFS) spectroscopy. In this study, we have investigated the preparation of arsenate-adsorbed ferrihydrite with the purpose to compare its structure to that of Fe(III)-As(V) co-precipitates and scorodite (both amorphous and crystalline). Furthermore the solubilities of these Fe(III)-As(V) solids are measured as a function of pH. Their structures are elucidated and correlated to their solubilities and thereby the application of these findings to the practice of arsenic removal and disposal is assessed.

Jan 1, 2003

By Takayuki Ichikawa

Hydrogen storage properties of ballmilled mixtures composed of the hydrogenated nano-structured carbon (CnanoHx) and lithium hydride (LiH) were examined by thermal and optical spectroscopic analyses. LiH needs higher temperature than 600°C for hydrogen desorption even under vacuum condition, while CnanoHx, which was mechanochemically synthesized from graphite powder by ballmilling under hydrogen atmosphere, reveals hydrogen and hydrocarbons desorption in wide temperature range from 300 to 800°C. Nevertheless, the composite of CnanoHxand LiH prepared by ballmilling desorbs hydrogen in relatively lower temperature range from 150 to 450°C. These phenomena indicate that the thermally liberated hydrocarbon radicals immediately react with LiH and release hydrogen instead of hydrocarbons emission, because CnanoHx contains hydrocarbon groups at the edge of nano-meter sized graphenes, which are recognized as IR active C-H stretching mode, and LiH is well-known as an ionic crystal. Furthermore, it is of interest that a nanostructural feature persists in this composite even after annealing at 350°C, which shows excellent cycle properties as hydrogen storage media.

Jan 1, 2006

By Roberto Parra

The wear and corrosion phenomena in the furnace lining of the ferrous and non ferrous pyrometallurgical processes are complex problems where chemical, interfacial and mechanical phenomena are presents. The characteristics of the processes determine the conditions to which these materials are submitted, where the thermal conditions reached during the operation is one of the most important parameter. Assuming that all the degradation phenomena are thermal activated, the rate of the different steps of the wear mechanism will depend on the thermal field in the lining. In view to apply the independent physicochemical knowledge of degradation mechanisms to the analysis and design of furnace lining the methodology of the Nodal Wear Model (NWM) was done. It combines the mathematical modelling of the heat transfer in the lining with the physicochemical control equation for the wear-corrosion phenomena. The NWM has been applied to different examples: theoretical analysis, laboratory scale test and industrial applications. We present in this paper the theoretical background of the model and two examples of applications: the sole of an electric furnace and the earth of a blast furnace.

Jan 1, 2006

By Rainer Köster, Tobias Wagner, Markus Delay, Fritz Hartmann Frimmel, Wolfgang Ferstl, Wolfgang Höll

"The mobilization of contaminants from industrial residues like ashes from municipal solid waste incinerators in case of leaching is investigated world wide. In classical leach tests only soluble species are considered. In addition the geochemical behaviour of residues has to be completed by assessing the mobilization via colloidal particles. This transport is well known from natural aquatic systems. Quantification of aquatic colloids is associated with considerable difficulties, because they are often found in low concentrations and in a size distribution where small particles with diameters below 0.1 µm predominate. In the past years, the Laser-induced Breakdown Detection (LIBD) has been developed as a novel sensitive method for quantifying colloids. Column leaching experiments with directly coupled LIBD were used to quantify the release of heavy metals and colloids out of bottom ashes. Some typical colloid bound heavy metal concentrations in the leachate are in some cases exceeding the limits defined by German authorities. The LIBD with a flow-through cell allowed to assign absolute values to colloid size and concentration."

Jan 1, 2008

By M. M. Salari Rad

An investigation of gold distribution in the mill products of Sar Cheshmeh beneficiation plant demonstrates that on average 44% of the gold is routinely recovered as a by-product in the copper concentrate, and the remaining is lost to the tailing. In order to evaluate the causes of gold losses, the distribution and mode of gold occurrence in the Sar Cheshmeh ore and mill products were studied. Searching for gold within samples and within individual grains of sulphide minerals was carried out by SEM in the backscattered electron mode and SIMS, respectively. The mineralogical distribution of gold revealed by microbeam techniques were combined with the results of relevant metallurgical experiments including, sizing, heavy liquid separation, and diagnostic leaching tests, and the nature and location of gold in the ore and mill products were determined. The combined results of the experimental approaches pursued suggest that while there are some gold in solid solution and/or -colloidal size within sulphides of the Sar Cheshmeh ores, "visible" gold is the principal form of gold occurrence at Sar Cheshmeh.

Jan 1, 1999