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By Akira Yazawa

The similarities and differences in copper, nickel and lead smelting processes are discussed based on the sulfur-oxygen chemical potential diagrams and the free energy minimization assessments using a thermodynamic software. The prominent features of copper smelting are ascribable to the fact that copper has a strong affinity for sulfur but weak for oxygen and the liquid phase immiscibility between Cu and Cu2S. During the oxidation of sulfides, nickel metal is not stable except at temperatures higher than 1500°C, well miscible with its sulfide, and is oxidized more easily than copper. Metallic lead looks as stable as copper during the oxidation of the concentrate but Pb and PbS. are much more miscible with each other and the vaporization loss is considerable. In the reductive smelting of oxides, the effects of oxygen potential and temperature on the copper contents in slag are not significant due to the monovalent character of copper and the reduction of copper content in slag is not easy in practice. The effect of the slag compositions on the oxidic metal contents of slag is much more significant for lead than either copper or nickel. Due to the immiscible nature between Pb and Fe, high grade lead bullion is easily obtained and lead is more tolerant to impurities.

Jan 1, 1998

At its Copper Cliff Smelter, Inco Limited processes a bulk copper-nickel concentrate in two Inco oxygen flash furnaces, The furnace matte is converted to low iron matte for further processing, and the molten converter slag is recycled to the flash furnaces. The flash furnace slag is discarded. Natural gas or coke supplies a minor proportion of the process heat requirements, thus limiting the flash furnace matte grade to the target 45% CuNiCo. Coke addition to the furnace offers a potential means of establishing a reducing barrier on the surface of the molten bath. Such a practice would be conducive to producing sulfur deficient (partially metallized) matte. At the same iron content, the iron activity of sulfur deficient matte is higher than that of regular matte. A supernatant coke barrier could, therefore, be expected to lead to higher nickel and cobalt recoveries, reduction or even elimination of magnetite furnace bottom build-up and increased sulfur elimination as S02 in the flash furnace. Preliminary experiments were conducted in a miniplant flash furnace to investigate the effect on process metallurgy of the suggested modified scheme. This paper presents the experimental results and discusses key aspects of the possible operation of the Inco flash furnace with a coke barrier separating the freeboard from the molten bath.

Jan 1, 2003

By Metehan Erdogan, Ishak Karakaya, Fuat Erden

"Mg-Ni system draws attention due to the promising hydrogen storage properties of Mg2Ni. The proposed method involves the use of NiO and MgCl2 in an electrochemical cell to from Mg-Ni intermetallics directly. The electrodeoxidation of NiO was followed by combination of Mg and Ni in molten salt electrolytes. The products were characterized by XRD analysis and SEM examinations. The quantitative results from Rigaku supported by Rietveld Refinement method conducted by Maud showed that more than 50 percent of the input Ni was converted to Mg-Ni intermetallics.INTRODUCTIONIt is well known that fossil fuels are the most common energy producing materials throughout the last century although, they are not renewable and their usage cause critical environmental problems [1, 2]. Hydrogen, on the other hand, is known as a clean, renewable energy carrier and instead of fossil fuels; usage of hydrogen for energy production will be the benefit of mankind. However, there are problems that hinder more common usage of hydrogen such as hydrogen storage [3]. Mg2Ni is known as Mg based hydrogen storage material with high hydrogen storage capacity [3-6]. Common Mg2Ni production methods are; mechanical alloying [8-11], vacuum induction melting [12, 13], vacuum arc melting [14], combustion synthesis [15], melt spinning [16], repetitive rolling [17] and isothermal evaporation casting [18] were also used. However, in all of these, pure Mg and Ni are required to be produced previously. Therefore, difficulties arise during handling, preparation and combination of Mg and Ni due to highly reactive nature of especially magnesium (i.e. oxidation of Mg) [11, 17, 19, 20]. Although hydrogen desorption dynamics can be significantly improved with usage of nanostructured Mg2Ni [7], it is difficult and it requires very long processing durations to produce nanostructured Mg2Ni by above processes."

Jan 1, 2014

By B. J. Elliot

The Outokumpu Oy flash smelting furnace was designed for a capacity of 69,5 mtph of concentrate. The history of developments on the flash furnace, from the original operating capacity of 55 mtph to a proven capacity of 115 mtph of concentrate, is summarised. The new feature of operation at BCL Limited is ?the use of screened lump coal reduction in the settler region of the furnace. This paper considers the effects of settler bath reduction on the furnace smelting capacity, the condition of the furnace ?lining and bath, and ,the slag losses generated from the flash furnace and ultimately to discard. By using the settler bath reduction technique the capacity of the furnace for smelting new concentrate has been increased by 15% and hearth accretion has been eliminated by direct reduction with coal, which has also allowed the generation of a substantial protective lining on the furnace walls and roofs. As a result of improved slag losses from lump coal charging the metal recoveries on the flash furnace have increased from 70% to 87% for nickel, 68% to 82% for copper, and 28% to 45% for cobalt.

Jan 1, 1983

By Geoffrey S. Plumlee

The Summitville gold mine, located in southwestern Colorado, received tremendous publicity in the 1980's and 1990's for leaks of cyanide solutions from its heap leach facility. As is typical with cyanide spills, real time, geochemically rigorous assessments of the environmental effects were not performed. Past United States Geological Survey (USGS) research used simple mixing experiments to model the influx of alkaline cyanide heap leach solutions from Summitville into a nearby stream, whose waters were highly acidic due to severe acid-rock drainage (ARD) from the mine. These experiments indicated WAD cyanide rapidly degraded due to formation of Fe-Cu-CN solids and lesser HCN volatilization. The alkaline heap leach solutions also precipitated hydrous iron-and aluminum, oxides and hydroxysulfates (iron and aluminum 'supplied by the acid. rock drainage (ARD]), which then sorbed copper and other heavy metals from the ARD. These results indicate that mixing of cyanide heap leach solutions with ARD may be a cost-effective remedial method at mine sites where treatment of both is required. New experiments are currently in progress to further refine a potential remedial process.

Jan 1, 1998

By Minji Jun

Leaching of the surface-coated metals from waste acrylonitrile butadiene styrene plastics (WABSP) has been investigated in the ammoniacal solution. The ammoniacal leaching of WABSP (typically containing 4.1 wt% Cu, 1.3 wt% Ni, 0.03 wt% Cr) efficiently dissolved copper and nickel, leaving unleached chromium as fine particles. The results indicate that the anions of different buffer media for metals leaching follow the order: CO3 2− > Cl− > SO4 2−. A declined leaching with high NH4OH–(NH4)2CO3 ratio (8:1) and a steep rise in extraction with high pulp in solution revealed the influence of anion (CO3 2−) and cation (Cu2+) present in the system. The leaching performed in carbonate solution by maintaining 5.0 M total NH3 concentration as NH4OH–(NH4)2CO3 ratio, 4:1; pulp density, 200 g/L; agitation speed, 400 rpm; temperature, 20 °C and time, 120 min yielded the maximum extraction (>99%) of copper and nickel. The study reveals a plausible recovery of the surface-coated metals from the WABSP without altering the properties of polymer material that can be recycled separatel

By Chan. C. L., Zehr. R., M. M. Chen, J. Mazumder

"Two three-dimensional models of a surface tension gradient driven flow during laser surface heating are developed. The first model is based on a perturbation solution. The basic solution corresponds to the stationary axisynwnetric case and perturbation is based on a small scanning velocity. The advantage of seeking a perturbation solution, as it turns out, is that the three-dimensional flow is modeled by two sets of two-dimensional equations which are presumably much more tractable than the original three-dimensional equations. Numerical solutions are obtained and discussed. The second model is a full three-dimensional numerical solution of the Navier-Stokes equations, using a point-by-point partially vectorized iteration scheme. Surface shape is also determined in a self-consistent manner. The effect of the presence of convection on pool geometry, cooling rate and solute redistribution is presented and discussed.IntroductionThe existence of fluid flow and convection and their effects were first reported in the fifties (1,2). The role of convection in controlling pool geometry such as pool shape, undercut and ripples, and defects such as variable penetration, porosity and lack of fusion and weld properties such as weld homogeneity and bead formation is studied by a number of researchers and is reviewed by the authors in a recent paper (3).Recently, surface tension gradient driven flow has been identified as one of the forces responsible for convection within the molten pool (4,5). It is postulated that surface tension gradient driven flow is responsible for the surface ripple formation in the weld pool (6-8). Oreper, et al. (9) developed a two-dimensional convection model. Buoyancy, electromagnetic and surface tension gradient forces were considered. The formulation was based on a specified pool profile. It was found that the surface tension gradient is the dominant force in most cases. However, the solid-liquid interface is not known a priori. In fact, the solid-liquid interface, i.e. the pool shape, is a piece of information that the model should be able to predict. A two-dimensional transient self-consistent (i.e. the solid-liquid interface is solved as part of the solution] model for laser surface melted pool was first developed by Chan, Mazumder, and Chen (3)). This model predicted a non-uniform cooling rate, hence non-uniform microstructure. Depending on the Prandtl number (i.e. material) and surface tension number, the shape of the molten region as well as the cooling rate changes. It was also predicted that the recirculating velocity is of one or two order of magnitude higher than that of the scanning velocity. This model provides the detail of the flow field and heat transfer on a plane perpendicular to the scanning direction. However, the front-to-back motion and its effect on heat transfer also play important roles in the physical process, especially for the fact that the recirculating velocity is so much higher than the scanning velocity. Such a motion cannot be obtained from two-dimensional models."

Jan 1, 1986

By Patrick R. Taylor

Ilmenite concentrate and methane are fed to a non-transferred arc thermal plasma reactor to produce a powder that is primarily TiC and Fe. This material has promising characteristics for powder metallurgy applications. Free energy minimization plots were used to predict the feasibility of the reaction. An estimate of the optimum molar ratio between the ilmenite concentrate and methane was made based on the mineral composition. Argon-helium mixtures were used as plasma gases. The effects of power input level, carrier gas flow rate, powder feeding rate, and methane-ilmenite molar ratio were studied and the behavior of the system characterized. Two different powder injection angles were tried. A mathematical model to describe the temperature profiles in the reactor was formulated and solved. The product has been characterized by x-ray diffraction and atomic absorption. A conversion of 97 % of Ti to TiC was achieved. It was found that minor amounts of titanium oxides, iron carbide and free carbon are also present. TEM and SEM were used to study the morphology.

Jan 1, 1996

By D. J. Droppert

This paper describes the precipitation-production of crystalline scorodite (FeAs04.2H20) from arsenic-rich sulphate-based metallurgical solutions at ambient pressure (95°C). Arsenic is precipitated by means of a controlled precipitation technique in which the supersaturation of the solution is carefully controlled. By controlling the supersaturation in the presence of seed material. the formation of amorphous ferric arsenate is prevented. Scorodite is known to be the most stable As(V) compound and is therefore preferred as host mineral for arsenic immobilization. The effect of the following parameters on the preCipitation behaviour and kinetics of scorodite are discussed: Type of base seed concentration initial [As]. sulphate concentration. neutralization rate. seed recycling and method of Fe(ll!) addition to Fe-deficient arsenic solutions.

Jan 1, 1996

By Daniel K. Kim

The charge for the copper refinery is a mixture of anodes produced at San Manuel from BHP source concentrate and copper purchased from external sources. Control of unwanted impurities in the tankhouse - is very important and beneficial. Currently available removal/recovery technologies were reviewed for the control of bismuth and antimony levels in the electrolyte. Recent studies have focused on solvent extraction (SX) technology and generated successful results for the removal and subsequent recovery of bismuth and antimony. The SX system employs the reagent, ACORGA SBX-50, in conjunction with a patented high chloride stripping system. The latter enables recycle of the eluant, avoiding the high costs associated with conventional systems, such as regeneration of resin. Concerns over potential transfer of organics and chloride ion to the electrolyte were readily addressed, solved and demonstrated using conventional, established technology. This paper describes the benefits of electrolyte purification, the flexibility afforded by the SX system, the operational practices necessary for maintaining adequate control of bismuth and antimony impurities in the electrorefining environment and possibilities for future development /exploitation of the Zeneca SX system at the San Manuel refinery.

Jan 1, 1998

By Katja Reinharter

Arsenic can be found in different sulfidic copper concentrates and residues, which for several years have commonly been used in copper metallurgy, as the “arsenic-free” resources are getting rare. Due to the high toxicity the removal of arsenic in the copper smelting process is a very important topic. The typical chemical slag and sulfur attack on the refractory material is getting enhanced by the presence of arsenic. This work deals with post-mortem investigations of a magnesia-chromite brick and castable used in copper smelting furnaces showing an additional and increased chemical attack by arsenic. The knowledge on the wear behaviour is not only based on a detailed chemical and mineralogical characterization, but also on thermochemical FactSageTM calculations, which are carried out on provided post-mortem samples. Post-mortem investigations on used refractory materials represent an important prerequisite for the product development, as well as for special engineered lining concepts to support our customers.

By Yuanyuan Zhang, Patrick J. Masset

"The reduction of FexO in slag is one of the fundamental reactions in iron and steelmaking technology, including the blast furnace process (BF). Experiments on the reduction reaction of iron oxide using CaO-SiO2-Al2O3-FexO-C mixtures were carried out using thermogravimetric analysis (TGA) under reducing conditions at temperatures up to 1100°C. The composition of the primary slag was chosen so that the FexO concentration varied between 0 and 75 wt % and the CaO/SiO2 ratio being kept constant to 0.90. From the TGA curves recorded isothermally at different temperatures the kinetic parameters of the iron oxide reduction were determined.IntroductionIn blast furnace the iron ores and coke are charged in layers from the top. The reduction of iron oxide by coke is one of the fundamental reactions in the blast furnace process. Although a great amount of work has been done on the topic of reduction of composites [1, 2, 3], gasification of carbon [4, 5] and reduction of iron oxides by CO [4, 5, 6], the mechanism of reduction in iron oxide - carbon powder mixtures is not fully understood. Fruehan [1] and Rao [2] studied the reaction rate of the reduction of iron oxide by different types of carbon and concluded that the reaction mechanism is controlled by the oxidation of carbon at temperatures up to 1200°C. Rao [2] studied the reaction of hematite with graphite as carbon source up to 1080°C. An activation energy close to 300 kJ/mol was calculated within the temperature range of 950°C to 1087°C. In his study, Fruehan [1] determined the rate of reduction of Fe2O3 and FeO by coal, coke and coconut charcoal as carbon sources within the 900°C to 1200°C temperature range. He found that the reduction of Fe2O3 by carbon occurs in two stages and that the reduction of Fe2O3 to FeO is faster than that of FeO to Fe. This is due to the fact that the CO2/CO equilibrium ratio is higher, and hence, the rate of oxidation of carbon is faster. Fortini and Fruehan [3] have studied the reduction reaction of wustite by graphite and wood charcoal. They found that the wustite reduction can have a significant effect on the overall rate of reduction in composites at high temperatures or in the presence of a large excess of carbon. The calculated activation energy of the reduction reaction by wood charcoal was close to 368 kJ/mol, while the activation energy of the reduction reaction by graphite was 444 kJ/mol."

Jan 1, 2011

By Fumio Hashiuchi, Yushiro Hirai, Masatoshi Maeda, Toshihiro Nagata

"Increase in the copper smelting capacity at Saganoseki Smelter & Refinery was attained through various improvements in the PSconverters and the flash furnace. Two of the major innovations in the converting process were: a new operational technology which avoids increase in the copper content in the converter slag even when higher copper grade matte (65%) are treated in the slag making stage and a technology which shortens the operational interruption time which is caused by coolant charging. The latter was realized by introducing a new automated coolant charging system with which it was made possible to charge the coolant without stopping the blowing into the converter. These improvements brought about a remarkable increase in · the production capacity per converter and an annual production of 450,000 tons of copper without adding new furnaces was made possible. In addition, good results have been obtained of the tests with modified tuyeres to further increase the production.IntroductionIn a bid to renovate its Saganoseki Smelter & Refinery and to establish a leading production unit in terms of global competitiveness, Nippon Mining & Metals undertook major restructuring efforts since 1994. One of its themes was the shift from· a two-flash furnaces operation to a single-flash furnace operation. The shift was successfully completed in 1996 while maintaining the production at the same level (330,000 tons per annum of copper). Then, the productivity was enhanced to 450,000 mtpy without adding new furnaces through technological and operational improvements. It is now planned to increase the smelting capacity further to 470,000 mtpy this year.Some technological and operational improvements in the matte converting process and the new plan resulted from the tests with modified tuyeres are presented in this paper."

Jan 1, 2000

By Arthur E. Morris

Fifty years ago when Professor Yazawa began his career, the field of process simulation and modeling was in its infancy. Since then, tremendous progress has been made in our ability to model metal production flowsheets from mine to refined metal. This progress has come about by parallel developments in basic understanding of process chemistry and in computational techniques. This paper will review the progress made in process understanding and modeling in lead, zinc, and copper metallurgy from its inception to the present, and the role of Professor Yazawa's work in furthering this progress. Specific examples wi1\ be given for the sintering of lead concentrates, slag fuming, zinc concentrate roasting, flash smelting of copper, and pyro-extraction of zinc. Factors limiting further progress will be described.

Jan 1, 2003

By Xun An

Slag from an electric slag cleaning furnace was injected with methane and air mixtures to facilitate the recovery of copper and cobalt. The effects of methane-to-air ratio, gas flow rate and temperature on the reduction and metal separation were investigated. The results showed that over 90 percent copper and up to 60 percent cobalt could be recovered from the slag with a gas utilisation of around 70 percent, as calculated by thermodynamic simulation. Methane-to- air ratio was a major factor affecting the rate of reduction under the present experimental conditions. Further, injection of gaseous reductants greatly enhanced the coalescence and settling of entrained metal droplets. A reduction mechanism is proposed and the factors influencing the coalescence of copper droplets are discussed.

Jan 1, 1998

By S. Seetharaman

A mathematical model has been developed to evaluate the viscosities of melts at high temperatures. The viscous flow in liquid is described by the equation, {n = Aexp(AG*/RT)} based on the absolute reaction rate theory. The Gibbs energy of activation,{ AG* } is considered to be a function of the temperature as well as the composition of the melt. The model has been applied successfully to various metallic and slag systems from unary to quaternary. On the basis of this model, a relationship has been suggested to relate the Gibbs activation energy of viscosity to the Gibbs energy of mixing in binary metallic melts. The viscosities predicted from available thermodynamic data in the case of a number of binary metallic systems using this correlation show satisfactory agreement with the reported experimental values.

Jan 1, 1994

By Mark Tsirlin

Kinetics of the initial oxidation stages of diffusive silicide coatings on 8 molybdenum and niobium at 1100 - 1700 and under the pressure of 400 and 1330 Pa has been studied using methods of gravimetry and gas phase analysis of oxygen, as well as by SEK, XRD and EDMA methods. The first oxidation stage described by asymptotic equation in case of NbSi coating changed over to the stage described by parabolic equation. The asymptotic law was shown to depend on non - stationary conditions on the oxide layer boundaries. Interconnection between silicides and quartz structures, on the one hand, and peculiarities of oxidation kinetics, on the other, is [discussed. The possibility of estimation oxygen atom jump frequency in quartz and fractions of oxygen reacting with metal and with silicon proceeding from the analysis of the kinetic data was ascertained. Conditions of oxidation kine- tics transfer from asymptotic (or parabolic) stage to a non - protective "linear" stage, associated with volatile ~roduct formation, are also discussed.

Jan 1, 1995

By Barry Welch, Kai Grjotheim

"The capital intensive nature of the present process for aluminium smelting, the low productivity per unit reactor, and pressure to reduce the electdcal energy demand have motivated the search for an alternative process. Optional routes include carbo-thennal reduction of alumina (using an alloy phase immediate), chlorination followed by electrolysis of aluminium chloride, and electrolytic decomposition of alumina using inert electrodes. Materials performance and reactor design constraints have been a major limitation for alternatives. However parallel research has led to considerable advances in the process efficiencies and scale of both the Bayer process and the Hall-Heroult cells.Future development of alternatives is dependent on breakthroughs in Materials Science such as the development of stable conducting anodes and stable wettable cathode materials. However if successful it is probable that some spin-offs will be retrofitted to existing cells. Therefore the basic Hall-Heroult technology will continue as the dominant process for at least the next half century.IntroductionThe present Bayer/Hall-Heroult process for production of aluminium is just over 100 years old. Frequently, during the century of its technological development questions have been raised as to whether it is the ideal route for metal production. The questioning was particularly intense in the period between the mid-1950s and the mid-1060s when the limitations of the Hall-Heroult electrolytic stage were evident. Then the cells were only 30 to 35 % efficient with respect to the utilisation of the hydro-electricity (requiring 16 18 kWh/kg, thus making it strongly dependent on cheap electrical energy), while the size of cells being installed were 80 to 130 kA. Hence the process was capital intensive, the productivity per reactor volume low, and the process was labour intensive (requiring about 15 man hours per tonne of aluminium). In addition, the use of pitches for Soderberg anodes and the fluoride electrolyte were creating problems through emission. At that time material science had paid little attention to the manufacture and use of carbonaceous materials or the development of alternatives that were corrosion resistant to cryolite or liquid aluminium. Hence cell lives were short - typically 600 to 1000 days - thus adding to operating costs. Thus the grass over the fence, as foreseen in 1960s vintage crystal balls appeared much greener for alternative processes."

Jan 1, 1988

By Alexander Burns

Electrolytic salt splitting is a technology where acid and/or base is regenerated from a neutral salt using membrane electrolysis. Recent advances in the understanding of brine treatment, membrane stability, and cell design have made electrolytic salt splitting feasible on certain hydrometallurgical solutions. Meanwhile, environmental regulations have made the bulk disposal of salt solutions more difficult. In this paper, sodium sulfate salt splitting is examined from a cost perspective, compared to purchasing the reagents directly. Relative costs are estimated for several regions based on published electricity and reagent prices. The results show that salt splitting is economically favourable in some regions, and can be made more favourable by applying modifications to the traditional three-compartment desig

By James P. Bennett

EAF slag chemistry and its control have been recognized as important in producing quality steel at a low price for a number of decades_ EAF steel producers make lime and dolomite additions to furnaces, controlling the CIS ratios and sulfur pickup from the steel. Existing phase diagram data at 1600°C for CaO, MgO, FeO, SiO2, and Al2O3 was used to write a computer model optimizing slag chemistry for slag foaming and reduced refractory wear. The model, its development, and its use in an industrial steelmaking environment will be discussed along with how the model can improve energy efficiency. The importance of EAF mass balance to account for critical materials like Si in scrap and refractory wear using the model will also be emphasized_

Jan 1, 2003