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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 E. Ilgar

"Deposition studies were conducted in acid copper electrolyte to determine the influence of chloride ions on cathode morphology. A statistically designed screening test was carried out in the absence and presence of 20 ppm CI- using a three factor, two level factorial design, in an electrolyte containing 36 gl'! Cu2+ and 150 gl-! H2S04, The independent variables evaluated were agitation; current density and temperature and their influence on surface roughness was determined. The copper deposited at current densities where activation was the primary control mechanism appeared similar in morphology whether stirring was used or not. The addition of 20 ppm CI- to the electrolyte gave rougher deposits under the same conditions. In the mixed control regions, considerably rougher, dendritic deposits were obtained when CI- was present. Agitation was effective in reducing the copper surface roughness both in the apparent activation and mixed control regions in the presence ofCI-. The results of this study showed that 20 ppm Cl- polarized the copper deposition at low overpotentials but caused depolarization at higher overpotentials.IntroductionChloride ion is inherently present in copper electrolyte, either as an additive or from other sources such as make up water. The behavior of the chloride ion is well documented in electrorefining operations, but its role in copper winning is less obvious. However in both cases there is evidence that cathode growth and solution chemistry are strongly influenced by its presence. The mechanism and electrochemical action of the Cl"" have been shown to be very complex, therefore a better understanding of its influence on electrocrystallization is essential for improved cathode deposit growth control. It was proposed that Cl"" polarizes the copper deposition reaction at low concentrations due to CuCI formation but depolarization occurs at higher concentrations due to the formation of a soluble CuCI2"" complex [1,2]. Franklin [3] reviewed the mechanism of additives in the electrodeposition process and proposed that the Cl"" complexed with copper, adsorbed on the cathode as an induced anion leading to an increase in the reduction rate. At cathodic overpotentials less than 100 mY, lppm NaCl had a polarizing effect, i.e. an increase in impedance of the charge transfer step. At higher Cl"" concentrations up to 100 ppm, depolarization occurred as evidenced by a decrease in impedance, which was attributed to soluble cuprous complexes [4]."

Jan 1, 1997

By Tomas Astorga

APEC, the Asia Pacific Economic Cooperation is the forum of 21 countries having approximately 56% of the total world income, and over 45% of global trade. In 1997, APEC economies produced 67% of the world copper output, 55% of gold, and over 45% of other base metals. Mining in APEC captures more than 60% of the total mining investment in the world. New and emerging economies are now appearing in the demand scenery, such as China. New trends in the international environmental regulations are posing questions related to the use of copper in different industrial and consumption applications. These may have a strong impact on future trade of copper. New applications are also appearing based in new technology fields. The paper examines the growth potential of the copper market in main consumer ad highly populated economies of APEC, incorporating analysis of various interrelated factors. It also analyses the outlook of the copper supply. Its conclusions point to the need to implement demand outlook models. Finance and economic reforms will open important avenues for trade growth in basic metals, particularly copper. Changes in the consumption patterns of highly populated countries will add to better perspectives of copper demands. The recovery of a fast pace of economic growth in the APEC region will bring new demands for copper, especially as a consequence of high tech applications. More extended policies focused in the need for developing energy efficiency programs and schemes will add to this picture.

Jan 1, 1999

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

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

Jan 1, 2012

By Zbigniew Smieszek, Ryszard Chamer, Ryszard Prajsnar, Zygmunt Kurek

"Lead-containing wastes processed at the IMN’s Division in Legnica originate mainly from dry and wet dedusting installations of the technological lines for copper production. These are lead dusts and lead-zinc dusts characterised by the specific properties resulting from the chemical composition of the Polish copper concentrates. Besides lead, they contain many accompanying metals and impurities such as zinc, copper, sulfur, chlorine, potassium, sodium, and also bituminous substances. Processing of lead-containing dusts is conducted in the installations of rotary-rocking furnaces heated with gas-oxygen burners fitted with auxiliary systems for cleaning process gases and refining re-circulating dusts. The processing technology utilizes innovative process and technical solutions enabling disposal of lead-containing wastes from copper metallurgy and from non-ferrous metals industry according to the BAT recommendations and to the guidelines specified in integrated permission. In this paper, the main technological aspects of processing lead-containing dusts at the IMN’s Division in Legnica have been presented.IntroductionCrude lead is obtained in Polish lead metallurgy from various primary and secondary materials, such as Zn-Pb concentrates, lead-bearing dusts of copper metallurgy and battery scrap. In zinc smelter Miasteczko Slaskie S.A. crude lead is produced from sulfide and oxide Pb-Zn concentrates in ISP process. Orzel Bialy S.A. and Baterpol Ltd. produce crude lead in short rotary furnaces in the process of smelting products of mechanical battery scrap separation– desulfurised or not desulfurised paste and metallic fraction. KGHM Polska Miedz S.A. and IMN Divison in Legnica produce crude lead in rotary furnaces in the process of smelting of polymetallic dusts and slimes from copper production processes."

Jan 1, 2008

By Roger Altman

The solubility of copper in primary spinel crystals encountered in reverberatory slag samples has been determined by electron microprobe analysis. These spinels, which ranged in composition from 22% A12O3 to pure magnetite, contained small quantities of dissolved copper (0-0.4%). Based on literature data it was estimated that the solubility limit of copper in solid magnetite is no greater than about 1% at 1200°C and about 2% at 1250°C. However, it was found that practically every spinel crystal examined contained significant amounts of matte inclusions. Further examination of converter slag revealed large quantities of irregularly shaped precipitated magnetite crystals which contained a large proportion of copper inclusions. Additional experimentation showed that the total copper content in reverberatory slag samples was greater than the sum of the estimated en- trained plus dissolved matte in the slag. This difference is believed to be significant and is due to the presence of matte inclusions in the spinel crystals. In the present reverberatory slag samples these inclusions accounted for about 1/2 of the amount of sulfide directly entrained in the slag.

Jan 1, 1976

By Fiseha Tesfaye, Pekka Taskinen, Daniel Lindberg

Due to increasing complexities of raw materials for base metals production the conventional pyrometallurgical processes are challenged. To make the appropriate modifications, thorough evaluations of the thermal stabilities of phases and phase assemblages which are commonly encountered in these processes are essential. In this work, phase relations and thermal stabilities of equilibrium phases in the Cu-Ni-S system have been reviewed. The calculated phase diagram of Cu-Ni system has been validated. At T < 630 K, in the Ni-rich corner, large scatter in data has been observed and discussed in detail. The other binary systems, Cu-S and Ni-S, have been also critically reviewed together with the ternary Cu-Ni-S system. The reviews were focused on compiling and discussing phase relations and thermal stabilities of the selected systems in the pyrometallurgical processes of Cu and Ni productions.

Jan 1, 2016

By Sang-Beom Lee

For thermodynamic prediction, the deoxidation equilibrium of aluminum in Fe-36%Ni alloy was studied with a cold crucible under Ar gas atmosphere at 1773K. For the deoxidation reaction in liquid Fe-36%Ni base, i.e.: A12O3(s) = 2A1 + 3O The interaction parameters and the equilibrium constant between aluminum and oxygen in liquid Fe-36%Ni alloy are given in the following: eo Al = -3.8, roA1=0.9, eAl° = -6.4, rAl° = 700, rAIAIo = 3.1, roA1o = 833 within the composition range of [Al] < 1 mass%. The temperature dependence of the equilibrium constant was obtained in the range of 1773K < T < 1973K by using reported data and present results as follows: log KAo= 0.58-24463.7 / T The deoxidation equilibrium with aluminum in Fe-36%Ni could be thermodynamically well described in the range up [Al] < 1 mass% with first and second order interaction parameters as well as the equilibrium constant determined in this study.

Jan 1, 2002

By A. Jakobsson

Studies of the rate of interdissolution in oxide systems in the solid state are of importance in materials processing through the powder-metallurgical route. As there is a need for following the rate of the such reactions continuously, a new method based on high temperature X-ray diffraction was developed. Mechanical mixtures of the oxides were placed in a high-temperature X-ray diffraction unit and the changes in the intensity and position of the peaks with highest intensity for both the components were followed as functions of time. A suitable theoretical model has been developed in order to interpret the experimental data and evaluate the diffusion coefficients. The method was applied in the case of the system MgO-NiO. The results obtained are compared with those obtained by another new method, based on solid-state galvanic cell technique with calcia stabilized zirconia electrolyte, developed in the Department of Theoretical Metallurgy. The advantage of the present techniques to monitor the progress of the reaction continuously make them suitable for computer control of such processes.

Jan 1, 1995

By R. J. Chesher, J. C. Anzalone, T. F. Krusmark

The BHP Copper Refinery at San Manuel, AZ employs conventional electro-refining technology, plating at a current density of 335 A/m2 on six kilogram copper starter sheets. In 1995, a combination of variable anode chemistries and increasing current density in the tankhouse created periods of increased bismuth in cathode. Bismuth in electrolyte was minimized by bleeding electrolyte to the nearby BHP leaching facility. However, the expected drop in cathode bismuth was not achieved. Investigations indicated that starter sheets contained a significant concentration of bismuth. The bismuth was found to occur in combination with antimony on the surface of the sheet adjacent to the mother blank. Studies were conducted to determine the mechanism by which Group VB elements are incorporated into the starte sheets. Operational practices were introduced to minimize bismuth in starter sheets and improve cathode quality.

Jan 1, 1997

By Jun Iwai, Osamu Takai, Yasushi Inoue, Hiroyuki Sugimura

"Infrared reflection absorption measurement was performed during plasma-enhanced chemical vapor deposition of silicon dioxide films at room temperature. Hydrocarbon contaminants adsorbed onto growing film surface are oxidized by oxygen radicals in plasma resulting functional groups which include C=O and C-O bondings. These groups exist only near the surface and are hydrolyzed rapidly after exposure to air.IntroductionRecently low-temperature silicon dioxide (SiO2) deposition has been in a growing industrial demand in pa1ticular, polymelic substrates such as polycarbonate and polyethylene telephthalate, which have poor heat resistance, need low process temperature (near room temperature) in coating of SiO2 which is a suitable material to improve optical and mechanical properties of polymenc products. Plasma enhanced chemical vapor deposition (PECVD) using organosilicon reactants is one of the most promising technique for lowering process temperature, so that it has been extensively studied1-12. In the present; however, hydrocarbon contaminants and a plenty of Si-OH termination in Si-O-Si networks tend to exist in the films, which degrade mechanical, optical and electrical properties of the films. It is necessary to understand the deposition mechanism at, low temperature in order to solve the problems. We have studied the low-temperature PECVD of Si02 by spectroscopic diagnosing techniques such as optical emission and mass analysis6-7, 11- 12Infrared reflection absorption spectroscopy (IR-RAS) has been a well-established technique for characterization of thin films on metals as· well as on semiconductors and insulators13-17. In this paper, we report on' the surface reaction of room-temperature PECVD of Si02by using in situ IR-RAS."

Jan 1, 2000

By Chang Wei, Zhigan Deng, Yizhao WANG, Cunxiong Li, Gang Fan, Xingbin Li

During the process of hematite precipitation, the transformation of Na jarosite convert into hematite has been studied in a batch reactor at different temperatures, ranging from 170°C to 200°C with 3h of the retention time in the presence of 30g/L Fe ( ) and 4g/L Na+. The composition of precipitation was seriously depended on the temperature, at 170°C hematite and sodium jarosite are the reaction products of iron precipitate, with an increasing in reaction temperature the sodium, sulfur content in precipitated decreased and sulfur mainly exist in forms of SO4 2-, and when temperature over 200°C hematite was the only phase in product. An increasing temperature was not only beneficial to iron precipitation, also conducive to jarosite conversion to form high quality hematite precipitate.

Jan 1, 2016

By Joseph Hamuyuni, Pekka Taskinen

We present experimental results for the liquidus in the system Cu2O - CaO -Al2O3 at 1250 oC. In this study, we quantified the liquidus by the equilibration/quench/analysis technique, with Cu2O, Al2O3, and CaO as primary materials exclusively. Experiments were conducted in air at an at oxygen pressure (p) = 21.3 kPa). Equilibrated specimens were quenched in brine solution of 10 wt% NaCl. We then quantified the liquid chemical compositions by means of Energy-Dispersive X-Ray Spectroscopy (EDS) and Electron probe micro-analyzer (EPMA). This study reveals inconsistences in liquidus surface of the present ternary diagram of the system here in mentioned. Differences of up to 10 wt % compositions of the species have been observed.

Jan 1, 2015

By Hongfa Hu, Stavros A. Argyropoulos, Stephan Ferenczy

"Physical as well as mathematical modeling was carried out to investigate the exothermic mass transfer in liquid metal systems. In these systems, the exothermicity induces unique heat, mass and momentum transfer phenomena. Moreover, these phenomena are deeply coupled and they are further complicated by the presence of a moving boundary.In the physical model used, ice cylinders were immersed into sulfuric acid solutions, because the intermixing of ice with sulfuric acid is very exothermic. In this low temperature system, velocity and temperature measurements in the sulfuric acid were made as well as measurements of the ice melting in the sulfuric acid.The mathematical model developed solved simultaneously the heat, mass and momentum equations numerically, utilizing the control-volume finite difference approach. The enthalpy method was adopted to track the moving boundary. Predictions made by the mathematical model were in close agreement with the results obtained by the physical model.The results from the mathematical model were further validated with experiments involving high temperature liquid metals. Specifically, data were obtained in an experimental setup involving (a) dipping silicon cylinders into high carbon liquid iron and (b) dipping nickel cylinders into liquid aluminum. Results from these experimental studies supported the predictions of the mathematical model."

Jan 1, 1999

By Xiaorong Liu

Interfacial emulsion generated in copper solvent extraction is an inhomogeneous O/W emulsion that consists of organic phase, aqueous phase and solid particles. In order to determine what kind of components in organic phase promotes the emulsion, the organic phase separated from the interfacial crud provided by Dexing Copper Mine in Jiangxi, China was analyzed for its components by combined gas chromatography-mass spectroscopy. It was found that many kinds of emphiphiles containing such hydrophilic groups as carbonyl, carboxyl, or acylamine existed in organic phase, most of which were originated from the reagent degradation. Conclusively, Lix984N would degrade gradually during a long-term contact with the acidic aqueous feed and strip reagents. Lix84 and nonylphenol, as effective components of Lix984N, degraded almost completely after long-term recycling. As a result, the effective components of Lix984N were far lower in concentration than the dense-aromatic impurities derived from the diluent and the degradation products in total. The degradation of Lix984N would deteriorate solvent extraction, disengagement performance and result in more serious interfacial emulsion.

Jan 1, 2006

By B. Erik Ydstie, Tor Lindstad, Vianey Garcia-Osorio

"As a result of the high temperatures present in a Carbothermic Aluminum Process the content of aluminum and aluminum sub-oxide in the gases leaving this process is high. These gases as well as energy must be recovered. In a Vapor Recovery Unit were the aluminum compounds react in a series of Heterogeneous Non-catalytic Reactions forming solid, liquid and gas products. The different product phases depend on the temperature present in the system. In this work we present dynamic model of the Vapor Recovery Unit of a conceptual Carbothermic Aluminum Process. Because of the complexity of the system several models are developed and coupled to capture the essential physics of the multiphase reaction problem. A Shrinking Core Model describes the reaction mechanisms. Then material and energy balances are coupled with the thermodynamics properties from the FACT database of thermodynamic properties, resulting in a system of nonlinear Partial Differential Equations. In the paper we describe the model development and governing equations for the reaction mechanisms and fluid flow. Finally we review the numerical schemes created for the solution of the model system. The model can be used for control and design purposes.IntroductionThe Carbothennic Processes for producing Aluminum can be divided into two groups (Motzfeldt et al. (1989)) In the first approach pure alumina is produced and reduced to pure aluminum. In the second approach an alloy (e.g. aluminum and silicon) is made and then aluminum is produced from the alloy. The history of both processes has been described by Ginsberg et al. (1965). At least three aluminum producers began largescale testing of this process in the 60's Alcan, Pechey-Ugine and Reynolds. Alcoa did some smaller scale experiments.Alcoa was one of the first companies to produce aluminum by Carbothennic Reduction (Foster et al. (1956)) and US Patent 2,829,961 April 8, 1958. In this process a carbon containing molten aluminum phase was a floated on top of an oxy-carbide melt. During the cooling the dissolved carbon deposited as aluminum carbide. The carbide was then separated from the molten aluminum by a fluxing agent. This process was successful but economic unfeasible."

Jan 1, 2001

By G. A. Irons, G. S. Hanumanth

A three-dimensional mathematical model for the electric furnace of Cominco's Kivcet process was developed to compute the electric field intensity, power dissipation, temperature and velocity distributions in the furnace. A number of simulations of the electric furnace operation were carried out for various electrode immersion depths and electrode currents. The results showed that the current penetrated the bullion layer, generating high current densities in a layer approximately 0.3 m thick located in the slag/bullion interface region. An increase in the electrode immersion depth increased the furnace power as well as slag temperatures, and generated more vigorous bubble stirring and thermal homogeneity in the slag. For a given applied current, the computed power was in reasonable accord with the measured power input. The calculated temperatures were in rough agreement with the tapping temperatures of slag and bullion.

Jan 1, 2000

By M. Nishikawa

The Hachinohe Smelter employs the Imperial Smelting Furnace (ISF) for production of zinc and lead and handles a large number of concentrates and recycled materials. In recent years, recycled materials such as zinc-bearing materials, lead sludge and Waelz oxide have provided up to 30% of the feed materials at the plant. To allow for a satisfactory operation using such a wide range of recycled materials, the Hot Briquetting Plant was built in 1986 and started its operation in January 1987. In April 1988 the zinc production capacity of the ISP was increased from 81,000 to 101,000 tonnes per year. The additional production in the ISP has been attributed to the utilization of the hot briquetting process. This paper describes the various facts of the smelter, concentrating on hot briquetting operations and treatment of hot briquettes in the ISF.

Jan 1, 1991

By B. S. Boyanov

The hydrometallurgical technology for zinc production in Bulgaria is characterized by the use of considerable quantities of imported zinc concentrates and several kinds of Bulgarian ones which are quite different in chemical, phase and granulometric compositions. In this connection, 7 sulfide zinc concentrates (Bulgarian and imported ones) were investigated by chemical analysis, DTA, TGA, X-ray diffraction analysis, sieve analysis. The accomplishment of optimal mixing of concentrates and providing stabile mix composition for a long period of time of roasting in fluid bed furnace is a task of primary importance in the technological process control in zinc hydrometallurgy. This can be achieved using mathematical optimization methods.

Jan 1, 2006

By Olga K. Karakasi, Angeliki Moutsatsou, Ioanna Kavallari

"The present study focuses on the amelioration of the behaviour of high calcium fly ash (HCFA), investigating its application in a new environmental field: oil spill clean up. High calcium fly ash is a by-product of electric power plants, produced annually in large quantities, whose greater amount is landfilled. Some of its properties, such as its chemical and mineralogical composition, its fine particle size, its porosity, floating ability and hydrophobic character make it an attractive material for this purpose. Researches showed that when added to an oil spill, it forms a semi-solid phase, which allows the quite total removal of the oil, but it is not stably retained on the surface. In order to ameliorate its floating ability, the decrease in its specific gravity by mixing with a lighter material is investigated. In the present study the mixing with two materials, already used in oil spill clean up, sawdust and a polymer, has been examined. Addition of 15-25% w/w sawdust to HCFA results in a material with better performance than HCFA or sawdust alone: it has a satisfactory floating ability and allows total removal of oil. Addition of the polymer, however, has resulted in no significant amelioration of the oil sorption behaviour of HCFA, probably because no affinity between HCFA and polymer has been achieved.IntroductionCoal fly ash is a by-product of coal combustion in electric power plants, produced worldwide in huge quantities, approximately 500 million tones annually. High calcium fly ash (HCFA) is classified to class C presenting a (Al2O3 + SiO2 + Fe2O3) > 50%. The production of lignite fly ash in Greece comes up to 13 million tones annually, of which only 12% is used in construction applications, the other being landfilled [5, 6].Besides its limited application worldwide as a construction material, research is focusing on the development of new environmental applications, such as waste stabilisation and solidification, soil and water environmental improvement [9, 12]. For the application of fly ash in further environmental fields several chemical modifications have been applied, in order to improve its properties. Extensive research has been focused on the conversion of both coal and lignite fly ash to zeolite and its further application in environmental field, such as the uptake of inorganic (heavy metals and ammonium [8, 11]) or even organic compounds (methylene blue [15]) from waste water streams, or the use as molecular sieves, to adsorb water molecules, SO2 and NH3 from gas streams, due to the high cation exchange capacity and porosity of the produced zeolithic material. Furthermore, lignite fly ash has been combined with sodium silicate solution, prepared by treatment of rice husk ash, and tetrapropylammonium bromide, to synthesise hydrophobic zeolite ZSM-5 [4]."

Jan 1, 2008