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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

By Berndt Moeller

Mercury-cell chlor-alkali production plants generate mercury contaminated wastewater streams from which mercury must be precipitated and filtered, resulting in a sludge containing 2% mercury (designated KI06) that cannot be landfilled in the United States without treatment. REMERC is a chemical treatment process used to recover 99% of the mercury from wastewater sludge generated at these plants. The process uses leaching to oxidize mercury compounds to mercuric chloride, washing and filtration to separate mercuric chloride from the treated sludge, and cementation to reduce the mercuric chloride to metallic mercury. Mercury not recovered in cementation is recycled to the wastewater process for precipitation and filtration. Treated sludge contains less than 260 ppm total mercury and 0.2 ppm TCLP, meeting the USEPA low mercury subcategory specifications that allow landfill disposal. REMERC uses readily available chemicals, is straightforward to control and inexpensive to operate, has no mercury emissions to air, and recovers metallic mercury. REMERC enabled significant cost savings including lower solids disposal costs, recovery and reuse of metallic mercury in the chlor-alkali process, and ability to treat non-wastewater sludge. No new EPA permits were required. REMERC was shown to be a viable process for recovery of metallic mercury from K106 designated sludge.

Jan 1, 2003

By J. Lui

The 15m high Inco flash furnace uptake was designed as a reaction chamber with the objective of destroying the H2S contained in the furnace off-gas by combustion with oxygen at about 1300?C. Until recently, the oxygen required for this purpose was injected through afterburners located at the bottom of the uptake. An undesirable side effect of this practice was the formation of build up accretions on the inside walls of the uptake. This buildup had a negative impact on both the furnace on line time and the control of the flash smelting process. In late 200 I, the afterburners were relocated to the roof of the uptake. As a result, about 80% of the uptake accretion buildup disappeared with obvious beneficial effects for the operation of the furnace. This paper discusses key flash smelting aspects that affect the operation of the flash furnace uptake such as the dusting rate, the formation of H2S in the freeboard of the furnace, and the impact of using coke to supply some of the heat required by the process. The mechanism of buildup formation and its dependence on uptake afterburners location are also examined. Prof. Yazawa&apos;s sulfide smelting thermodynamic relationships proved instrumental in understanding the conditions that influence the formation and the elimination ofH2S and uptake buildup.

Jan 1, 2003

By Irsan Chandra

It is generally recognized that the gold thiosulfate leaching system requires the presence of copper and ammonia in order for acceptable leaching kinetics to be observed. However, the presence of copper and ammonia complicate the chemistry of the system as thiosulfate is rapidly oxidized by oxygen under these conditions. In addition, the environmental impact of ammonia would need to be considered before the adoption of this system. This paper describes fundamental studies into the thiosulfate oxygen system. The two reagents for this system are thiosulfate and oxygen, and leaching is carried out at pH < 7. It will be shown using electrochemical techniques that both the reduction of oxygen and the oxidation of gold-to-gold thiosulfate are hindered. Thus, if leaching is to work under these conditions, then both half reactions need to be improved. The use of additives, such as thiourea and lead have been shown to dramatically improve the oxidation of gold and the reduction of oxygen respectively. The leaching of gold in the presence of such additives is discussed.

Jan 1, 2003

The standard procedure of fire refining consists of sulphur removal via air injected through tuyeres, arsenic slagging via soda-lime flux and oxygen reduction by air or oxygen deficient air or a steam fuel mixtures. The use of porous plugs to stir with an inert gas has been mainly considered as a surface renewing agent that increases the product quality and shorten the refining cycle. In the present study the effect of the bottom stirring by nitrogen gas injection through porous plugs for the treatment of the crude copper in the range of 400-150 ppm sulphur, 3,000-2,000 ppm arsenic and 14,000-7,000 ppm oxygen content was investigated. The combined effect stirring-reducing, by the use of air or a steam fuel mixtures through tuyeres for oxygen removal, follows a kinetics of first order where the constant, K, can be represented by the following polynomial expression: K = A * R2 + B * R + C Where A, Band C are constants that depend on the nitrogen flow rate and R is the air-fuel ratio or the steam-fuel used in the reducing step. Depending on the optimization of the flow of nitrogen and the air-fuel or steam-fuel mixture and only if just the oxidation, complexing and reducing steps are considered, the process cycle might be shortened by 45%.

Jan 1, 2003

By Akira Nishikawa

During the twentieth century, the copper smelting industry achieved dramatic expansion corresponding to the vast growth of global economy. This was largely due to innovations in pyro-metallurgical processes, such as autogenous smelting and continuous smelting and converting technologies. However, as copper production capacity increased, its impact on the environment also could not be ignored, and thus with increasing global environmental awareness, many smelting operations either had to renew or rebuild their facilities. In addition to these changes, in places like Japan and Europe, with scarce primary resources, the treatment and recovery of metals from a variety of items such as car shredder dust, used electrical appliances and electronic devices, on top of scraps traditionally treated, is having a profound effect on the reduction of waste and the preservation of primary resources. Thus compared to the days when copper smelting focused on the environmental control in order to break with "Smoke Stack Industry", copper smelting today is making an important contribution to the sustainable development of human society.

Jan 1, 2003