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By Masatoshi Ogasawara

Saganoseki smelter & refinery operated two flash smelting furnaces, producing a combined 330,000 metric tons per year (hereinafter mtpy) of copper. [n 1996, however, it successfully shifted to a single fumace operation while maintaining production at the same level. Since then, the production capacity has been further increased to the present 470,000 mtpy by technological improvements. Also, in order to reduce the converter load which represents a bottleneck in efforts to increase production, the matte grade was gradually increased and currently runs at 65 to 66% attaining the low copper content in the slag (hereinafter slag loss) of 0.7 to 0.8%. This ' paper introduces some improvements, recent operation results and thermodynamic analyses.

Jan 1, 2003

By Kenneth L. Driggs

The Environmental Protection Agency's Clean Air Act? of 1970 provided the driving force for the current Magma Smelter configuration. The historical and technical perspectives of those process developments are reviewed?. Innovations in procedures and equipment have allowed compliance with the requirements of the regulating authorities?. The wet scrubbing of converter gasses and the monitoring of converter operations by a controlling foreman are two of the major contributors? to these successes. The Clean Air Act Amendments of 1990 have posed many new concerns? for all U.S. industry, including the few (seven) primary copper smelters remaining. Future concerns include tightening the sulfur dioxide ambient ?Standard from the current three-hour averaging period to one hour.

Jan 1, 1992

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

By M. Wallin

Millions of tons of sludge from different metallurgical processes are produced worldwide annually, and the environmental impact of landfilling these often hazardous sludges stresses the need to understand their role as valuable resources. The current work explores the potential of producing a saleable low-phosphorous ferromanganese alloy by utilizing sludge from the silicomanganese industry together with an iron source. The aim of the project is to explore the feasibility and practical challenges related to reduction and dissolution of manganese and silicon from the sludge to liquid metal and slag. Parameters such as ratio of input material as well as the effect of adding limestone and coke to the mixture were explored by thermodynamic calculations and adapted experimentally. Results show that a ferromanganese alloy, in fact, can be formed, while silicon and calcium forms a complex slag that captures a significant amount of impurities.

By Ilija Ilic

Recovery of tin from tinplate and production of good-quality detinned-plate for further processing in ironworks has been the subject of interest for many years. Tinplates are mostly used for production of tin containers for food industry and consumer goods. The research carried out so far included determination of the parameters of dissolution of tin from tinplates by alkaline solution of NaOH and electrochemical recovery of tin from the alkaline solutions. During leaching, NaNO3 and methanitrobenzoic acid (MNBA) as oxidants were studied. By leaching the waste tinplate which contains 0.31 % of tin with a solution of 1.12 mol/dm3 NaOH, 0.26 mol/dm3 Na2CO3 and 0.09 mol/dm3 MNBA at temperature of 70°C for 60 mm, a degree of tin leaching of 97 % was attained. MNBA facilitates oxidation of Sn2+ into Sn4+ suitable for obtaining compact, and not spongy, Sn cathode deposit, as it was the ease earlier. Recovery of tin by electrolysis from solutions obtained by leaching was studied to determine the effect of electrolyte composition on the quality of cathode deposit and the degree of electric current efficiency. Experimental results obtained at a laboratory level were checked on an enlarged laboratory set up where continuos leaching of tin from waste tinplate and its electrolytic recovery from the solution obtained were carried out. The experimental set-up -operated under semi-industrial conditions, and about 500 kg of waste tinplate was processed yielding about 1.160 kg of tin (99 % Sn).

Jan 1, 2000

By Gregory A. Knapp

Treatment of industrial wastewaters generally advances with specific chemical concentration and mass-flow targets, established by National Pollutant Discharge Elimination System (NPDES) permits. Treated discharges must also address toxicity to test and receiving water organisms. Various parameters might need consideration during treatment design and planning, such as the known toxicants, hardness, alkalinity, solids, nutrients, metals in both the dissolved and particulate state, and even flow. Since toxicity is used as a "catch all" regulatory monitoring tool, design of treatment systems should focus on the various factors contributing to toxicity.

Jan 1, 1996

By G. C. Yao

Branch and needle-shaped intermctallic compounds of iron, silicon and aluminum normally exist in the molten aluminum. If a suitable amount of manganese metal is added into molten aluminum, the shape of the intermallie compound particlcs may become lumpish and spherical. According to the difference in electric and magnetic properties of these impurity particles and molten aluminum, these impurity intermctallie compound particles can be separated by applying an alternating magnetic field. In this experiment the alternating magnetic field was formed by a "C" type loop with AC (50Hz) current. The inner vacuum of the fireclay refractory separator is 25>< 15" 130mm3 with a lateral baffle inside. The separator was put into the interspace of the "C" type loop. It was found that the longer the separation time, the larger the amount transferred of impurities. The amount of transferred impurities increases with the increase of separation time and intensity of magnetic field. The addition of manganese metal enhanees signifieantly the efficiency of impurity separation.

Jan 1, 2003

By Takahiro Miki

In order to use metallurgical grade silicon (MG-Si) as a starting material for solar cell, phosphorus has to be removed from silicon because phosphorus is a n-type dopant. On the other hand, silicon, ferrosilicon, and silicomanganese are widely used as deoxidizers in steel refining processes. Since most of the phosphorus introduced during the deoxidation process is brought into final products, it is important -to lower the phosphorus content of these alloys. Hence, thermodynamics of phosphorus in such metals is important for the evaluation of dephosphorization processes. In the present study, thermodynamic properties of phosphorus in molten Si-P alloys at 1723- 1848K and those of Si-Fe-P and Si-Mn-P alloys at 1723K have been determined by equilibrating respective metals in a controlled phosphorus partial pressure. The results are expressed as follows.

Jan 1, 1998

By D. F. Suarez

Spontaneous nodulation leading to growth of well developed glossy spheroids (generally hemispheres) of up to 0.06 cm width in 120 min has been observed during copper electrodeposition with certain levels of glue, thiourea and C1-. Thiourea alone can produce spontaneous nodulation but addition of glue and/or Cl- is required for rapid and sustained growth. In most cases once the glossy nodules develop they consume the majority of the copper deposited; thus, the specific current densities (and hence copper electrodeposition rates) on the glossy nodules are about an order of magnitude or, more greater than on the adjacent planar surfaces. The texture of the adjaoent planar surfaces is not glossy in appearance but is well faceted showing the usual deposition grain structure for such additives. Cathode potentials when spontaneous nodulation occurs are about TOO my more negative than with usual copper electroplating. This fact associated with evidence of extremely high levels of cathode surface passivation based on cyclic voltammograms indicates that the conditions which lead to spontaneous nodulation result from a very tightly adsorbed additive surface film. This film breaks down in specific points initiating the glossy nodules which then grow at extremely rapid rates. Current density is also important in spontaneous nodulation. At equal deposition times a current density of 21.5 mA/cm produced much larger glossy nodules than at 48 mA/cm2. The surface concentration of the glossy nodules was much greater in the latter case, however. The role of current density is still not well understood. The role of it as well as the relative roles of the three additives, thiourea, glue and Cl- in spontaneous nodulation is presented. Preliminary results and some possible correlations of these to help explain spontaneous nodulation are presented. It is believed that tankhouse upsets where cathode nodulation occurs may be related to this phenomenon.

Jan 1, 1987

By Lenny Winkel

With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates research on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite (CuzS) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS2) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO2, it also alters the behavior of volatile impurities during decomposition of copper sulfide concentrates. Chemical eqUilibrium calculations for chalcopyrite contaminated with enargite (Cu3AsS4) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation from intermediate sulfides. The need to better assess the potential of direct sulfide decomposition has prompted the development of an experimental setup for studying the decomposition reactions. The experiment has been devised such that data on the decomposition kinetics and on impurity removal can be obtained at temperatures up to 2500 K.

Jan 1, 2003

The results of laboratory, large-scale laboratory and commercial scale investigations regarding the process of slag melts cleaning by oxidizing-reduction gas mixtures with a wide range of Po2 and the use of matte of various compositions as an extracting phase are presented. The copper, nickel and cobalt behavior during the cleaning process has been studied based on SEM and x-ray Microprobe of the quenched slag melts. The general cleaning mechanisms have been found. On the basis of the obtained data the most efficient cleaning methods have been proposed.

Jan 1, 2003

By Jonkion M. Font

Due to the known disadvantages of the use of iron silicate slag in the nickel converting stage, i.e., high metal losses, high magnetite content, and low fixation of impurities in the slag, the development of the new proposed "ferrous calcium silicate slag" for smelting and converting processes of nickel is very promising. Hence, considering the successful experimental results of using CaO base slag for the nickel smelting process, a study based on a detailed comparison for the phase equilibrium, and the minor elements distribution between the Ni3S2-FeS matte with either FeOx-CaO or FeOX-Si02 base slag was investigated. The main results are summarized as: no difference in the nickel losses between both slags was found at high nickel content in the matte, and the fractional distribution analysis for arsenic and antimony pointed out their preferential fixation in the calcium ferrite slag rather than in the iron silicate slag. Considering the energy and pollution issues, the technical feasibility of using calcium ferrite slag in a converting process of the Bessemer matte will have a prominent future for the nickel industry.

Jan 1, 2003

By M. El Ganaoui, P. Bontoux

"A computational model to investigate solid/liquid phase change transitions for binary alloy under directional solidification is presented. Conservation equations are developed by using an homogeneous formulation. A second order accuracy method of time and space based on finite volume approximation has been evaluated by comparing results to spectral solution for time-dependent solutal convection developping in a melted alloy. For extended model to solid/liquid interface effects time amplification of solutal perturbation injected near the interface is described before considering solutal convection is melt.IntroductionThe enthalpy method gives a front fixing approach for energy equation without introducing coordinate transformation. The interfare position is recovered a posteriori [1]. A number of authors have extended this approach so as to include the convection phenomena within the two phase 'mushy region' [2, 3, 4, 5, 6].We have developed a time-dependent enthalpy-porosity formulation for directional solidification [4, 6, 8]. The interaction between solid and liquid phases is modelised by a Darcien type force in the phase change area. The behaviour of the melt is similar with the flow of an incompressible fluid in a porous medium. This force is proportional to the relative phase velocity. It corresponds to a damping force depending on the anisotropic permeability of the 'mushy zone'. The permeability depends on the liquid fraction and on the size of·solidification microstructures. An informative discussion of a new slant on the general approach of continuum mechanics needed to analyze the formation of mushy zone is given in [12]. The method is extended to the presence of species diffusion: the solutal Stefan condition which expresses the solute incorporation or rejection across the interface is accounted implicitly in a species equation valid in all the domain [14, 15]."

Jan 1, 2001

By M Philip Schwarz

"This paper reviews the status of computational modelling of a variety of common metals reduction processes, namely the blast furnace, rotary kiln and fluidised bed, and one new process not yet commercialised, namely smelting-reduction as in the HIsmelt Process. In each case, the last decade has seen the emergence of the capability to simulate the processes using multi-phase reacting computational fluid dynamics techniques. In some cases this capability is still in the process of being developed, and the next few years will see the maturing of the modelling techniques. As they become established, it will be possible to apply them to further refine the older technologies such as blast furnaces and rotary kilns, and assist in the optimisation, commercialisation and acceptance of the newer technologies such as fluidised bed and molten bath reduction. The development of a computational fluid dynamic model of bath smelting-reduction is described in some detail to illustrate how a large number of complex and interacting phenomena can be successfully simulated within a CFD framework. IntroductionPyrometallurgical reduction processes, such as the iron blast furnace, have become increasing more sophisticated through the centuries, so that today they are often highly efficient. There are continuing pressures, however, to refine existing processes and develop new ones. The imperatives are often economic, given that the long-term trend in the price of metals is always downward. In recent times, there has been the additional need to improve the environmental impact of metal production. Given that they almost inevitably require the use of carbon, metal reduction processes are large sources of greenhouse gases, and even a relatively small improvement in efficiency can be valuable in reducing CO2 production. Local environmental issues, such as the need to control of particulate emissions, are also driving incremental improvements in equipment.In addition to the economic and environmental drivers mentioned above, new process development is also being driven by the need to process new ores, and the need to produce unrefined metal in a form more compatible with alternative routes for downstream processing. An example of the latter is the production of DR! (Direct Reduced Iron) as a feed for EAF Electric Arc Furnace) in mini-mills.Further improvement of processes that have already been honed by continual plant experimentation over many years is not an easy task. To deliver further gains in efficiency, throughput, or product quality requires a highly sophisticated tool: one such tool· is computational modelling."

Jan 1, 2001

By Zhihong Liu

Monodisperse micron size nickel oxalate particles with rhombohedron morphology were prepared from condensed Ni(OH)2 suspension by a novel gel-sol process proposed by one of the authors. Firstly, condensed nickel hydroxide gel was formed by fast adding 1 mol dm-3 NaOH solution into 0.2 mol dm-3 nickel chloride solution, and then oxalic acid solution with a concentration of 0.25 mol dm-3 was dropped into the gel drop wise through a pump equiped with a pH controller under preset pH value, and in this process, Ni(OH)2 gel was converted gradually into monodisperse nickel oxalate sol. The formation of the nickel oxalate particles was found to proceed through a dissolution-recrystallization mechanism from the nickel hydroxide gel. The product particles exhibited rhombohedron like shape with micron size long axis and sub-micron size short axis. The effects of such factors, as temperature, surfactants, et al, were evaluated experimentally on the particles sizes and morphologies.

Jan 1, 2006

By G. Van Weert, A. van Sandwijk, O. W. J. S. Rutten

"Cathodic and anodic reactions in an acidic nitrate medium were studied in reference to the production of electrolytic manganese dioxide from pyrolusite' (Mn02) ores by reductive leaching. Two USA ores were investigated. The reductant for the pyrolusite ore is produced cathodically in an electrolytic cell and can either be nitrous acid (HN02) or nitric oxide gas (NO). In this work emphasis was placed on the nitrous acid leach. In a high-temperature leach in a nitrous/nitric acid medium, manganese and silver are solubilized and iron is not. Anodic electrowinning of manganese dioxide from the acidic manganese nitrate electrolyte yields flaky y-Mn02, similar to that produced from sulfate and chloride electrolytes. Cathodic regeneration of nitrorts acid was studied in a membrane cell in 1.0 M nitric acid and 0.0 to 0.1 M nitrous acid on a' platinized titanium cathode. At cathode potentials ranging from +950 to +700 mV (SHE), cathodic reduction to nitrous acid takes place, at cathode potentials < +700 mV, cathodic reduction of nitrous acid to nitric oxide takes place. A conceptual process is presented and discussed.IntroductionManganiferous-silver oresLarge reserves of manganiferous-silver ores are present in the Southwestern United States and Latin America. These ores are generally refractory to hydrometallurgical methods of treatment, due to the insolubility of the higher oxides of manganese (Mn 4+) in all common lixiviants such as cyanide solutions, dilute sulfuric acid, nitric acid, ammonia, salt solution, thiosulfates, etc. The silver is either bound by the insoluble manganese, or is rendered inaccessible to cyanide leach solution by the surrounding manganese mineralization.Higher oxides of manganese will dissolve if they are first reduced pyrometallurgically to manganous oxide (Mn2+). This is a widely used pretreatment for manganese dioxide ores and subsequent dissolution in sulfuric acid is common. In order to avoid the pyrometallurgical pretreatment with its large energy requirements and gaseous emissions, fully hydrometallurgical processes have been proposed. These processes are based on the presence of a reductant in solution, in order to reduce the insoluble higher oxides of manganese to soluble lower oxides. Aqueous S02 has been proposed and tested on industrial scale by the U.S. Bureau of Mines. After washing, silver could be extracted by cyanidation. The neutralization of the pulp prior to cyanidation however causes problems in filtration and the reagent consumptions are high [1]. More recently, acidified thiourea and bacteria were proposed for the solubilization of both manganese and silver in a single leach step. High extractions were obtained, but drawbacks of these methods are high reagent consumption or slow kinetics [2,3]. For the options of manganese recovery from the leach filtrate, precipitation with persulfate or ammonium carbonate and ion exchange have been proposed. The proposed options for silver reclaim are precipitation with either zinc or Na2S and adsorption onto activated carbon."

Jan 1, 1997

By Hong Yong Sohn, Miguel Olivas-Martinez, Zhixue Yuan

A novel flash ironmaking process that directly reduces iron oxide concentrate particles by gas is under development. The goal of this work was to study the possibility of reoxidation of iron particles in various gas mixtures. As the product iron cools down in the lower part of the flash reactor, conditions may become favorable for reoxidation because of equilibrium and high reactivity of iron particles. The effects of temperature (823 – 973 K) and H2O partial pressure (40 – 100 pct., Ptotal = 86.1 kPa) on the reoxidation rate were examined. The pressure dependence was first order with respect to water vapor, and the activation energy was 146 kJ/mol. A complete rate equation that adequately represents the experimental data was developed. For oxidation in O2-N2 mixtures, the effects of temperature (673 – 873 K) and O2 partial pressure (5 – 21 pct., Ptotal = 86.1 kPa) were determined. Reoxidation in pure CO2 was also investigated at 873 – 1073 K for comparison.

Jan 1, 2014

By T. T. Chen

Canadian Electrolytic Zinc has developed the "cement-stabilization of jarosite residue" Garofix) process to stabilize zinc plant jarosite residues for disposal. The cement-jarosite mixtures cure quickly, have good mechanical strength and low hydraulic permeability; they possess good neutralizing capability and chemical stability. In the jarofix process, Portland cement partly decomposes jarosite to form (SO4MOH)12.nH2O, ferric hydroxide and an alkali sulphate. Approximately 40% of the jarosite reacts in mixtures containing 30% cement. The jarofix product also contains various Ca-Al-Fesilicate-sulphate-hydrate phases and gypsum, which bond the individual particles together imparting mechanical strength and reducing the permeability. Most of the reactions take place in the first few hours of curing. Ammonium jarosite is slightly more reactive than sodium jarosite but releases NH3 gas; water-soluble Zn in the jarosite residue is stabilized in the cement reaction products.

Jan 1, 1996

By Sunil G. Warrier

A rapid infrared forming technique has been developed to fabricate titanium matrix composites. This technique applies infrared heating to infiltrate titanium alloys into carbon and silicon carbide prepregs. The entire process typically takes 1-2 minutes in an inert atmosphere. The advantages of this technique are that the process is fast, simple, does not require a vacuum or a high external pressure. The process is very economical both in energy conservation and operation costs. This technique has been used to produce void free composites with limited, well controlled fiber-matrix reactions and mechanical properties comparable to currently available titanium matrix composites.

Jan 1, 1993

By Mansoor Barati, Shaghayegh Esfahani

"The slag from extraction of ferrous and non-ferrous metals is a potential heat source which if treated properly can contribute to recovery of a significant amount of energy. The waste heat of slag may be used to generate steam, synthetic fuel gas, or electricity. Although several technologies have been investigated for this purpose, very little has been achieved in terms implementing the technology in industry. In this article, the development and application of various granulation techniques are reviewed and the methods to recover energy from granulated slag are discussed.IntroductionEvery year, more than 422 million tons of slag is being produced around the world as a by-product of the metal manufacturing at temperatures of up to 1300-1600°C [1, 2]. Currently slags are either disposed of or treated by processes such as granulation. Through the granulation process, most slags can be converted into a material which may be fully used as a cement feedstock. Conventional cement production is an energy intensive process with large emissions of CO2; therefore, the replacement can both be energy saving and environmentally friendly. However, for this purpose, the slag should have what is known as a “glassy” content (i.e. it should be amorphous) which requires rapid cooling rates that are not easily achieved due to the very low thermal conductivity. The main challenge in all these processes is to granulate the slag at a high cooling rate while the heat is also being recovered."

Jan 1, 2012