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By Corby G. Anderson

In nature, mercury is quite commonly found in association with antimony ores. This can be as a separate mineral such as cinnabar or in direct association with the antimony ore. The most common antimony-mercury mineral is livingstonite that occurs in places such as Algeria, Mexico, USSR and China. In the Roznava deposit in eastern Slovakia, tetrahedrite ore containing mercury ore has historically been processed pyrometallurgically for its silver and copper values. As well, in Tajikistan, major antimony deposits there contain significant mercury ore concentrations within the stibnite ore body. The mercury contained in these materials poses both a processing and environmental challenge. This paper will outline the processing of these types materials by industrial alkaline sulfide hydrometallurgical methods. The economics relevant to this potential application at Roznava in Slovakia will be outlined.

Jan 1, 2003

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of 873°K is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composition formed under roasting of concentrates with particle sizes less than 0.02 um (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CuFeSz2 each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forchamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By Huaming Yang

Infrared materials are a special kind of material widely used in military, biological engineering and chemical industry. However, the problems associated with them such as unstable properties, high cost and a high thermal expansion coefficient seriously restrict the development and the wide application of the traditional infrared materials with the SiC or ZrSiO4 matrix. The ultrafine quartz powder is normally used to prepare the infrared materials by hot-pressing technology. The aim of the paper is to investigate the thermal expansivity, the effect of the SiO2 size and the addition of Al2O3 or Fe2O3 on the infrared emissivity of the quartz matrix of the infrared material (QMIM) in a 8-25um wavelength range. The results indicate that 89% of infrared emissivity and 0.4x 10-5/°C of thermal expansion coefficient of QMIM can be obtained. The affecting mechanism of A1203 and Fe2O3 on the infrared emissivity of QMIM were also discussed.

Jan 1, 2003

By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and 1200°C. positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation Where negative deviations were observed.

Jan 1, 2003

By Peter Forschner

Classical Mixing Theory is based on applying many fundamental correlations to standard baffled dished bottomed vertical cylindrical vessels with high degrees of symmetry. Horizontal autoclaves operating at elevated temperatures and pressures have been used for more than two decades. All compartments and especially the first and last compartments are asymmetrical. To date no comparison of the effects of the asymmetric geometry on mixing system design and scale-up has been published. The results of investigating solids suspension, mixing time, momentum transfer from the impeller to feed slurry and feed inlet location in the first autoclave compartment are presented as influences on residence time distribution. CFD modeling was developed and verified with the test apparatus.

Jan 1, 2003

By J. E. Dutrizac

Fracture-exposed surfaces of sphalerite samples having five different solid solution iron contents ranging from 0.0 wt% to 14.8 wt% Fe were leached for 15 to 120 s at 100°C in 0.3 M Fe(S04)1.5 -0.3 M H2S04 media. The reacted samples were examined using X-ray photoelectron spectroscopy (XPS) which provides chemical state information on the first few nanometers of the solid surface. Surface compositions show that the leaching rate increases with increasing solid solution iron content of the sphalerite. Detailed evaluation of high resolution S2p spectra show that the leaching progresses via the formation of polysulphide species. Disulphide species were not detected in any of the experiments. Examination of the Zn2p and Fe2p spectra indicate little change in the chemical states of these elements over the duration of the experiments. Longer leaching times resulted in the generation of elemental sulphur. The ratios of elemental sulphur to dissolved ferrous ions and zinc suggest that less than 5% of the sulphide is oxidized to sulphate. Morphological studies showed that the elemental sulphur commonly formed at a few isolated sites, such as the grain boundaries. Furthermore, euhedral sulphur crystals were often identified. These observations suggest that at least part of the elemental sulphur forms via dissolved sulphide species which are oxidized in solution by ferric sulphate.

Jan 1, 2003

By C. Schwandt

Recent research work has led to the development of a new electrochemical hydrogen sensor, which is based on a proton conducting solid electrolyte in conjunction with a self-contained solid hydrogen reference standard and is operated at elevated temperatures. The incorporation of the internal hydrogen reference renders the sensor versatile and user-friendly and makes it attractive for practical exploitation. The present article focuses on the utilisation of the sensor as the integral part of a probe for the quantitative determination of hydrogen in molten aluminium and aluminium alloys. The main features of the sensor and the probe as well as the measuring technique are discussed. Experimental results obtained with the novel analyser in trials under industrial conditions are presented and highlight the good performance of the device.

Jan 1, 2003

At the present time, cyanide is the most widely used reagent to extract gold from its ores and concentrates. However, its use in mining has become the focus of intense attack by various groups throughout the world; as a consequence, a renewed effort has been launched to find suitable alternative lixiviants to recover gold. Chlorination was the most popular process to extract gold, before it was rendered obsolete with the advent of the cyanidation process at the turn of the last century, not least because it required the use of potentially hazardous and costly chlorine to oxidize/complex the gold. The PLASTOL® process, originally designed to recover the platinum group metals (PGM?s) from their ores and concentrates, provides an alternative to cyanide for gold ores. The process generates oxidizing conditions in the autoclave capable of forming the AuIII ion, and gold chloro-complexes result from the addition of small quantities (~5-10 g/L) of sodium chloride to the autoclave. The principles of the PLASTOL® process are briefly described, and several applications of the process to gold concentrates are presented. Various options available to recover gold from PLASTOL® leach solutions are also discussed.

Jan 1, 2003

By K. G. F. Janssens

In the process of annealing a deformed metal the microstructure changes due to concurrent recrystallization, grain growth and precipitation. It is common knowledge that all three of these microstructural transformations show a strong dependence on each other, and that an overall model must take the relevant interactions into account. Aiming at the development of an approach which is useful in the more general case, a computational model is being developed which allows the prediction of the three dimensional grain topology and orientation distribution function of any metal submitted to subsequent deformation and annealing, taking into account concurrent recrystallization, grain growth and precipitation and starting from a statistical representation of the deformed microstructure. In this contribution a case study is presented which illustrates the potential and limits of the state of the art in the field. Keywords: Microstructure Evolution Modeling, Irregular Cellular Automata, Deformation, Precipitation, Recrystallization, Grain Growth

Jan 1, 2003

By I. Van de Voorde

In this paper, results are presented concerning the search to implement Supported Liquid Membranes (SLM) Technology for the recovery of copper, nickel and zinc from electroplating and other effluents to prevent metal waste. A study of the influence of the individual parameters and of their combined effect on mass transfer in small-scale laboratory equipment has been performed, enabling to set forward the appropiate operating conditions for a pilot plant installation. The SLM pilot plant has been tested extensively, including short and long term runs, with real process solutions. It was demonstrated that the SLM technolgy is applicable for solutions containing 800 mg/L of metal ions, but also to the treatment of solutions with low metal content of origin other than plating shops. It was demonstrated by system analysis that the recycled salts are usable to produce metal electrolytes (for example Watt's nickel bath).

Jan 1, 2003

By Katsunori Yamaguchi

A new technique for the removal of tramp-elements from steel scrap has been required from the viewpoint of saving energy and protection of environment. In order to obtain fundamental information on the removal of copper, tin and zinc from molten iron, the extraction method by using of phase separation in the liquid Fe-Pb-C system was investigated at 1453K A mixture of iron, lead and carbon melted in a carbon crucible separates into two phases of lead and iron containing carbon. The compositions on the miscibility gap in' the Fe-Pb-C system are 95A%Fe-4.5%C-0.l %Pb and 99.9%Pb-0.1 %Fe. The distribution ratios of copper, tin and zinc between the lead and the iron phases, Lx=[masso/uX in molten Pb]/(masso/uX in molten Fe), are 2.2, 2.2 and lA, respectively. Seventy percent of copper and tin from iron scrap can be eliminated with comparable lead addition. Gold, silver and palladium are enriched in the lead rich phase, on the contrary platinum and rhodium are more distributed to the iron rich phase than to the lead phase.

Jan 1, 2003

Carbon injection into metallurgical slag is important in electric arc furnace (EAF) steelmaking for foamy slag practices and in nonferrous slag cleaning operations. The current publication presents kinetic data for coal injection into EAF slag to understand the interaction between injected carbon and metallurgical slag. Coal particles were injected into EAF slag and the kinetics were followed by gas and slag analysis. The results were analyzed, in terms of fundamental rate equations for each possible reaction step, as a function of temperature and slag composition.

Jan 1, 2003

By Christopher Gammons

In developing countries throughout the world, gold ores are being processed by mercury amal-gamation, a technique long banned in the U.S. - unless a retort operation is used for mercury recovery - due to mercury toxicity and its effects on the environment. Amalgamation is a simple process that involves contacting a ground, slurried concentrate or ore with mercury in a slightly agitated vessel, usually for several hours, The amalgamated mercury is separated by gravity and then filtered through a fine cloth to collect the gold amalgam as a sponge, which is then fired to remove the final remnants of mercury and produce high quality gold. However, in Peru and other developing countries in South America and throughout the world, tailings are simply discarded into uncontrolled drainages and ponds and the sponge is fired in the open air. Clearly, in this case, environmental friendly and, to make matters worse, is typically conducted by family members of all ages without proper protection. Furthermore, the technique is inefficient, yielding approximately 50% gold recovery. For the past two years, faculty members from Montana Tech in Butte, MT, USA and the Universidad Nactonal del Altiplano in Puno, Peru have teamed to study the La Rinconada Mine Complex located in southern Peru approximately 100 kilometers north of Lake Titicaca and 25 kilometers west of Bolivia. The mining complex is over 5,000 meters above sea level and exists at the foot of a receding glacier in the Andes Mountains. A suite of soil and water samples collected in 2001 documented extensive Hg contamination in the Rinconada area [1]. The present paper summa¬rizes a follow-up investigation in July-2002, in which water samples were collected at numerous locations along the 200 km length of the Rio Ramis, from the Rinconada mine com¬plex to Lake Titicaca, In addition, we report new results of Hg analyses of fish from Lake Titi¬caca, The results of this study have relevance to safety and health concerns for the miners as well as people in downstream communities.

Jan 1, 2003

By Tiffany Brown

In the thiosulfate gold leaching process, thiosulfate is used to complex gold following electrocatalytic oxidation of the native metal by Cu(II)-ammines. Unfortunately, Cu(II) complexes also catalyse the undesirable conversion of thiosulfate to polythionates. We have been seeking alternatives to ammonia, which fulfil the role of ammonia but minimize thiosulfate decomposition. One aspect of these studies has involved the determination of the rate of thiosulfate oxidation by the Cu(II) complexes from UV-Visible spectral changes. Various ligand classes, including pyridyls, polyamines, aminocarboxylates and picolinates, have been tested and the majority found to inhibit thiosulfate decomposition. Interesting variations in reactivity with the nature and denticity of the ligand and L/M ratio have been observed. In the case of open chain polyamine ligands with 2 to 5 nitrogen donors, the rate of thiosulfate oxidation was generally found to decrease with the denticity and the concentration of each ligand. Saturation of the Cu(II) coordination sphere appears to inhibit the oxidation of thiosulfate when excess thiosulfate is present. The Cu(II) complex of the branched polyamine ligand, tris(2-aminoethyl)amine (tren) exhibits this behaviour in excess thiosulfate. Interestingly, when the [Cu(tren)(OH2)]2+ complex is in excess oxidation of thiosulfate was observed. This unexpected finding prompted a spectrophotometric study of this reaction which has revealed that the oxidation of thiosulfate involves several processes, two of which involve the formation and decay of a tetrathionate radical.

Jan 1, 2003

By Hector Henao

To provide thermodynamic data for converting the nickel matte to liquid nickel, an experimental study was conducted in the phase equilibrium between the Ni-S alloy and the CaO-Ah03 based slag melted in a MgO crucible at 1873 K under controlled Pso2 of 10.1 kPa and pO;, in a range between 2.5x,IO,2 and 10.1 Pa by using CO-C02-S0Z gas mixtures. The content of nickel in the slag at POz of 10.1 Pa, above which solid NiO is expected to precipitate in the equilibrium state, was found to be 4.1 mass% and the contents of sulfur and oxygen in the nickel melt were 0.4 and 0.2 mass%, respectively. It was clarified that increase in the temperature reduces the solubility of nickel in the slag and the contents of sulfur and oxygen in the alloy. The distribution of minor elements such as gold, silver, copper, cobalt, iron, arsenic and antimony between the Ni-S alloy and the CaO-AI20) based slag was also studied. The distribution ratios of iron and cobalt, defined by (%X in slag)/[%X in alloy] where X is the minor element, are larger values than that of nickel, while those of copper, silver and antimony are similar to that of nickel. The distribution ratios of arsenic and gold are lower than that of nickel in the higher range of oxygen partial' pressure.

Jan 1, 2003

By Jesús L. Valenzuela

The solvent extraction for gold from alkaline cyanide solutions has been investigated using LIX 79 guanidine-based extractant. Different variables that could affect the extraction system were evaluated: equilibrium time, aqueous pH and extractant and modifier concentrations. The extraction isotherms of the aurocyanide complex with respect to other cyanoanions were compared and the following order of selectivity Au>Ag>Cu>Zn>>Fe was observed. From the pH isotherms it was found that aurocyanide can be extracted in alkaline media and a better separation with respect to other cyanoaniones was obtained in the range of 10.5 < pH < 11.2. Better selectivity was observed when using LIX 79 and tridecanol at 10% and 5% vol, respectively. Stripping gold from loaded organic was carried out at pH>12, using NaOH and NaCN solutions.

Jan 1, 2003

By Veronica Escobar

This paper presents results from a two month pilot evaluation of EMEW® technology at CODELCO Radomiro Tomic, in Chile. A prime focus in the test programme was to assess the technology?s capabilities to recover high quality copper from the Radomiro Tomic electrowinning tank house bleed stream. The EMEW® cell developed by Electrometals Technologies Ltd. tolerates substantially higher levels of contaminants than those found in conventional tankhouse, operating at high current densities while maintaining high cathode copper quality all the way down to low copper concentrations. To maintain high copper purity in a copper electrowinning (or electro-refining) tank house, a continuous bleed of solution must be taken from the tank house inventory to prevent build-up of contaminants, and resulting degradation in cathode quality. In an SX-EW operation, this bleed stream is normally recycled back to the solvent extraction circuit, but is occasionally sent to the raffinate pond to re-enter the leach circuit. Return of the bleed stream to the solvent extraction circuit creates a continually recycling load of copper in solution, which may reduce overall plant capacity and expansion potential. Return to the leach circuit has a similar effect, and methods to reduce its impact are always under consideration. The use of the EMEW® technology allows for direct and efficient recovery of near 100% of the contained copper instead of recycling. Tests were run at ambient temperature on bleed electrolyte using current densities which varied between 250 and 1100 amps per square meter, with copper concentrations between 38 and 1 g/l. A profile of maximum allowable current density with respect to concentration was developed, showing that high grade copper can be obtained at all levels of concentrations tested, by choosing an appropriate current density and electrolyte flow rate. The results of this programme show that the recirculating bleed electrolyte from an SX-EW operation can be converted into an expansion in copper production at a comparatively low investment cost.

Jan 1, 2003

By Hideki Yamamoto

A new technology to convert fluoride gas (C2H2F4 : R-134a) contained in the exhaust gases from semiconductor manufacturing plants and refrigerators directly into a harmless substance have been established, thus, presenting a new concept for the disposal of fluoride gases such as CFCs that are associated with the global warming. Experimental results verify that chemical reactions with metal compounds can take place at substantially lower temperatures of 700- 800K as compared with combustion treatment temperatures of 1200-1500K. The reaction product is mainly metal fluoride, which chemically is a harmless material. Furthermore, this process is compact, easily controlled, safe and has low running costs. This paper deals with a new chemical reaction method for the harmless disposal of gases effecting the global warming.

Jan 1, 2003

By K. Osseo-Asare

Rate laws for the hydrogen reduction of metal ions are typically of the form: [r = -d[M(II)]/dt = k[M(II)]xPy2H] where k is an apparent rate constant, [M(II)] and PH2 represent dissolved metal concentration and hydrogen pressure respectively, while x = 0 - 1 and y = 0.5 - 2. Half-order dependences have been reported for some M(II)/H2 systems; however, no satisfactory explanations have been offered. In an effort to bridge this gap in our understanding, the published precipitation rate data (for M(II) = Cu(II), Ni(II), and Co(II)) are reviewed (with emphasis on the reported reaction orders) and compared with the corresponding but limited electrochemical polarization data. Based on the available literature on the electrochemical kinetics of the M/M(II) and H2/H+ systems it is demonstrated theoretically that, under certain conditions (e.g., in the presence of electron-conducting solids), the rate of the M(II)/H2 reaction can be expressed as: [-d[M2+]/dt = k[M2+]2/1P2/12H] It is concluded that electrochemical processes probably play an important role in the hydrogen reduction of metal ions, especially for systems that involve heterogeneous catalysis.

Jan 1, 2003

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction, The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory-scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the determination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the determined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors determining the time of reduction.

Jan 1, 2003