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By S. Ajima

The Naoshima Smelter and Refinery is the most important copper operation of Mitsubishi Materials Corporation. There are a Mitsubishi Continuous smelter and a conventional type of copper tankhouse. The continuous smelter with 240,000 mtpy of anode production was commissioned in May 19914 replacing two existing smelters, i.e an original Mitsubishi Process line and a conventional reverberatory furnace line. In July 1992, the copper tankhouae was expanded for the purpose to close the gap of production capacity between the smelter and the tankhouse. The cathode production capacity was increased from 13,800 to 15,800 mtpm. By these plant modifications, the distribution of minor elements was significantly changed and the impurities load is getting on increase reflecting recent shortage of clean copper concentrates supply. The paper discusses the distribution of minor elements and the impurity control strategy at the smelter end the refinery.

Jan 1, 1995

By Jonkion M. Font

An expression for the distribution ratio of arsenic between slag and copper matte or liquid copper was developed by both, an extension of the Reddy-Blander moderl for deriving a priori the arsenic capacity, and by a relationship between the arsenic capacity and the arsenic distribution ratio. In this study, the a priori arsenic capacities in the FeO-SiO2, CaO-SiO2,MgO-SiO2, FeO-CaO-SiO2, FeO1.5-CuO0.5-MgO-SiO2, FeO-FeO1.5-CuO0.5-CaO-Mgo and FeO-FeO1.5-CuO0.5-CaO-Mgo-SiO2, slags were calculated at 1573 K. The a priori arsenic distribution ratio between the FeO-FeO1.5-CuO0.5-CaO-MgO-SiO2 slag and copper matte mn (Lx, )' and between the FeO-FeO1.5-SiO2 or FeO-FeO1.5-CuO0.5*-CaO-Mgo slag and liquid copper (Ls/cua) were calculated. The model calculated data are found to be in good agreement with the reported experimental data. The availability of reliable thermodynamic data for slag components and impurities in the slag-matte- metal system is essential for the accurate prediction of impurity capacities and distribution ratio data. The arsenic distribution ratio model developed here, can be extended for predication in multi-componet slags and mattes or liquid metal, and thereby may lead to the development of new slag systems for the efficient removal of arsenic in the copper smelting, converting and refining processes,

Jan 1, 2003

By Cheryl S. Lim

New technologies such as direct reduction and smelting reduction processes are increasingly being used in iron-making and steel-making in addition to conventional blast furnace technology. Critical parameters for control of these processes include the degree of metallization, degree of pre-reduction, and carbon and silica levels. On-line monitoring of these parameters is difficult because measurements often need to be made on hot ores (at or higher than -1000'C) in circumstances where representative sample streams are not readily accessible. A nuclear analyser has been developed which provides continuous, non¬intrusive, real-time measurements of iron, oxygen, carbon and silicon levels in hot ores undergoing reduction. The analyser has been tested in a plant using a direct smelting process on pre-reduced feed to the smelting vessel-, accuracies of 1% relative, 0.5 w'.96 (25% relative) and 1.0 wt.% (9% relative) were obtained for the degree of pre-reduction, carbon and silica respectively. The underlying method, capabilities and potential applications of the analyser will be discussed.

Jan 1, 2001

By Yichi Lu, Haydn N. G. Wadley, Douglas T. Queheillalt

"Using a 3-D ray tracing methodology combined with laser ultrasonically measured elastic constant data near the melting point, ultrasonic propagation in cylindrical single crystal bodies containing either a convex or a concave solid-liquid interface have been simulated and used to design new sensing concepts. Ray paths, wavefronts and time-of-flight (TOF) of rays that travel from a source to an arbitrarily positioned receiver have been calculated. Experimentally measured TOF data have been collected using laser generated/detected ultrasound on model systems with independently known interface shapes. Both numerically simulated data and experimental results have shown that the solidification (interfacial) region can be identified from ultrasonic transmission TOF data. Since convex and concave solid-liquid interfaces result in distinctively different TOF data. When TOF data collected in the diametral plane are used in a nonlinear least squares algorithm, the interface curvature has been successfully reconstructed and ultrasonic velocities of both the solid and liquid obtained. The reconstruction errors were found to be less than 5%.IntroductionMany of today's single crystal semiconductors are grown by variants of a vertical Bridgman technique in which a cylindrical ampoule of a molten semiconductor is translated through a thermal gradient, resulting in directional solidification and the growth of a single crystal, Fig. 1.1 It has long been recognized that during crystal growth the velocity and the shape of the solid-liquid interface, together with the local temperature gradient, control the mechanism of solidification (i.e. planar, cellular or dendritic), the likelihood of secondary grain nucleation/ twin formation (i.e. the loss of single crystallinity), solute (dopant) segregation, dislocation generation, etc. They thus determine the crystals' resulting quality.2-4 The solidification rate and the solid-liquid interface shape are also sensitive functions of the internal temperature gradient (both axial and radial) during solidification.5•6 This in turn is governed by the heat flux distribution incident upon the ampoule, the latent heat release at the interface, and heat transport (by a combination of conduction, buoyancy and surface tension driven convection, and radiation) within the ampoule. The solid-liquid interface's instantaneous position, velocity and shape during crystal growth are therefore difficult to predict and uncontrolled during growth, especially for those semiconductor materials with low thermal conductivity (e.g. CdTe).4-6 The development of technologies to non-invasively sense the interface position and shape throughout the vertical Bridgman crystal growth process has therefore become a key step toward developing a better understanding of the growth process, for enabling sensor-based process control, and thus ultimately for improving the yield and quality of difficult to grow semiconductor materials like CdTe."

Jan 1, 1997

By T. DebRoy

In recent years rapid technological advances have been achieved in the application of high energy density heat sources such as lasers and electron beams in diverse metals processing operations such as metal refining, fabrication, coating, surface modification and alloying. However, our phenomenological understanding of these new and emerging processes has not kept pace with the technological achievements. Inadequate understanding of plasma-metal interactions, the complexity of the component physical processes, and the scarcity of thermophysical data at temperatures much higher than the melting points of metals are the main difficulties in the comprehensive analysis of these processes. Several unique contemporary issues related to metals processing with high energy density beams such as rapid evaporation of alloying elements during processing and the role of plasma in influencing vaporization rate interfacial tension and species solubility in metals are discussed in this paper.

Jan 1, 1993

By George S. Dulikravich

An advanced semi-stochastic algorithm for constrained multi-objective optimization has been adapted and combined with experimental testing and verification to determine optimum concentrations of alloying elements in heat-resistant and corrosion-resistant H-Series austenitic stainless steel alloys. The objective was to simultaneously maximize a number of alloy's mechanical properties. This research will result in a rigorous tool for the design of high-strength H-Series steels and other types of alloys unattainable by any means existing at the present time. Such a material-by-design tool will also be able to reduce or minimize the need for the addition of expensive elements such as Cr, Ni, Co, Nb, Ti, V, etc. and still obtain the optimum properties of an alloy.

Jan 1, 2003

By Józef Czemecki

Polish copper concentrates are characterized by high levels of impurities, particularly Pb and As. Two technologies are being used for copper concentrate smelting at KGHM Polska Meidz S.A., namely the shaft furnace process (Legnica Copper Smelter, Glogów I Copper Smelter) and a single-stage process for direct to blister concentrate smelting in a flash furnace (Glogów II Copper Smelter). Both technologies are used at different physical and chemical conditions which results, in different impurities behavior. The paper presents flow sheets for copper production in a plant using the shaft furnace process and in another in which a single stage flash process is used. The metals distribution in particular semi-products is given as well as a method for elimination of impurities from the copper production cycle. Methods are also discussed for alloy and matte converting and copper refining to obtain low Pb and As concentrations in anode copper (0.3% Pb and 1500 ppm As maximum) that are being used in the KGHM Polska Meidz plants. Useful co-operation between the plants using different technologies, aimed at the limiting the effect of undesired impurities on the quality of blister copper produced, is also described.

Jan 1, 1998

By Baozhong Zhao

Laboratory experiments have been conducted on the removal of As, Sb and Bi from molten copper by SF 6 injection. The results showed that the impurities can be removed by SF6 injection in the? sequence of Sb >As >,Bi and the rate of Bi removal is affected significantly by the concentration levels of As and Sb in the copper melt. Analysis of the experimental data indicates that the impurity removal process is under chemical reaction control rather than by mass transfer of impurity through the molten copper phase. On the basis of experimental results, a kinetic model was developed and the order of chemical reaction and the volumetric chemical reaction rate coefficients of impurity removal were determined.

Jan 1, 1996

By O. Forsén

A new cell construction was designed for the study of the electrochemical behaviour of additives in conditions that simulate real copper, electrorefining. The behaviour of gelatine and thiourea was studied by applying different electrochemical methods, i.e. polarization resistance and voltametric measurements. In this study, individual galvanostatic electrolysis experiments were carried out for 120 hours. The organic additives were introduced to the electrolyte at certain intervals and their concentration was varied in the range &om zero to four ppm. An optical microscope was applied for the examination of copper cathode deposit microstructures. The results show that gelatine has a polarizing effect on the deposition potential of copper whereas even small amounts of thiourea depolarize the electrodeposition of copper. The maximum inhibitor efficiency of gelatine was obtained at a gelatine concentration of slightly lower than two ppm. When both gelatine and thiourea were present in the electrolyte, the depolarizing effect of thiourea exceeded completely the polarizing effect of gelatine. If chloride ions were added to gelatine and thiourea containing electrolyte, the electrochemical behaviour of the system was altered drastically. Chloride ions resulted in the prevailing of polarization effect caused by gelatine while the depolarizing effect of thiourea disappeared in this system. The polarizing effect of gelatine increased until chloride ion concentration of 30 ppm was reached. Also, the above electrochemical phenomena could be detected in the optical examination of copper deposit microstructure.

Jan 1, 1995

The cleaning of copper containing fayalite slag using a CuFe alloy was studied under an oxygen pressure ranging from 10-7 to 5 X 10-11 atm at 1200º c. The reduction of copper from fayalite slags by Cu-Fe alloys was found to be very effective. For example, at a P 02 of 10-7 atm, the copper content in the slag was reduced from 4.1 to 0.402 wt. percent after 90 min. of reaction time using a Cu- 5.27 wt. percent Fe alloy. The copper reduction rates were found to be independent of P02 in the gas phase when using Cu-Fe alloys which exhibit an iron activity of greater than 0.4. A mechanism for slag c1eaning is proposed based on the concept that the Cu-Fe alloy lowers the oxygen potential of the slag according to Eq.1 1, fol1owed by the reduction of cuprous oxide by wustite as shown in Eq.2. Here X represents element X in the alloy phase while (X) represents the element in the slag phase. The copper and iron transfer behaviour obtained in this study are explained by a ?Stepwise equilibrium model.

Jan 1, 1985

By S. Seetharaman

In the processing of molten metals, it is extremely important to monitor continuously the concentration levels of various minor elements, In the production of common metals like copper, iron and aluminium electrochemical sensors involving solid, as well as liquid electrolytes are being increasingly used to measure the concentrations of minor elements The present paper deals with the electrochemical principles underlying these measurements and the possible errors involved. One of the major difficulties in the case of the solid electrolytes is to correct for the consequences oldie electronic contribution to the conduction of the electrolyte. The application of the electrochemical sensors for molten metals processing involves designing of these probes to withstand the industrial operating conditions. In this respect, significant achievements have been made with respect to the design of oxygen probes for liquid metals in general and liquid copper in particular. Some of the salient design features are discussed in the paper, The application of auxiliary electrodes for impurities in molten metals like phosphorus in copper and silicon in iron are taken up. The development of oxygen sensors for slags is given special attention. Recent developments' in the field of sensor technology, as applied to metals processing are highlighted.

Jan 1, 1996

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts, The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10-7 atm. The concentration of CU2+ in such slags becomes significant at oxygen potentials of greater than 10-7 atm at 1300 °C. The activities of CuO0.5 and AsO1.5 in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of SiO2 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2x 103 cm2/s at 1350 °C and activation energy of 16 kcal/mol. Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300°C. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material,

Jan 1, 2003

By Hiroyuki Matsuura

The effects of P2OS or Na2O addition on the reaction rate of CO2 dissociation on the surface of FexO-base molten oxides was investigated at I 773K by isotope exchange method 1-6. The rate constant decreased with increasing P2Os content of molten oxides and the residual rate constant was observed at high P2OS content. On the other hand, the rate constant increased with increasing Na20 content for FexO-SiO2 melts, The rate constant was evaluated by the composition of oxides and the rate controlling step of CO2 dissociation was discussed.

Jan 1, 2003

By H. Yin, T. Emi

"Advantages of gas/flux injection technology as materialized in the main stay unit processes for steelmaking are depicted covering hot metal pretreatment through secondary refining. Current status of micro-kinetic issues involved in the injection technology are reviewed including gas-in- metal, gas-in-slag, flux-in-metal, metal-in-flux and three-phase dispersion systems with reference to macro-kinetics. Key problems are briefly addressed to further develop injection technology for steelmaking processes.1. FROM PAST TO PRESENTApplication of gas injection to steel industry started in early 1950's when inert gas bubbling via stopper rod, lance, or porous refractory plug was practiced to make the temperature of steel melt in ladle uniform The gas bubbling in ladle was then extended to slightly removing hydrogen ti'om the steel melt tapped from Electric Arc Furnace (EAF) and Basic Open Hearth Furnace (BOH) when vacuum processing facilities were not popular. Later, oxygen gas injection via calorized steel pipe into molten steel bath in BOH Furnace was also put into operation to promote the decarburization to increase the productivity of the process. This line of development has been made in parallel with more profound processes, i.e, top blowing Basic Oxygen Furnace (BOF) for primary steelmaking and side blowing Argon Oxygen Oecarburization (AOD) vessel for decarburizing stainless steels.On the other hand, injection of fluxes into steel bath was first industrialized in Germany in 1960's, Primary objective was to desulfurize steel melt in ladle by injecting CaC2 or CaCrCaO mixture via lance under neutral slag cover with good success. Difficulties in injecting fluxes without clogging and rippling at a desired flux/gas ratio, and durability of injection lance were resolved in due time to bring forth many injection facilities to flourish for versatile refining operation. Top injection of fluxes from main oxygen lance to BOF was also industrialized as LDAC to promote early slag formation. A new process then emerged which injects oxygen gas and fluxes together through concentric annular tuyere, installed at the bottom of the BOE into steel melt. This process, developed in Germany [Oxygen Bottom Maxhutte (OBM)] and brought into maturity in USA (Q-BOP) and Japan in a large scale operation, became the predecessor of the combined blowing (top and bottom blown) BOF which dominates modern steelmaking."

Jan 1, 1996

By Fiseha Tesfaye, Pekka Taskinen

"Thermodynamics of the equilibrium phase assemblage Ago_9Cul.lS-Cu2-xS-CuS have been studied by an EMF -method. The ternary phase was synthesized from the pure Cu2S and Ag2S in vacuum furnace at high-temperature and mixed with appropriate compositions of Cu2S and CuS to form the cathode electrode. The EMF-measurements were made on the solid-state galvanic cell Pt(-) I Ag I RbAg,ils I Ago9Cu1.1S-Cu2-xS-CuS I Pt(+), in a temperature range from 316 K to 498K.Based on the measured EMF vs. T relations, thermodynamic functions (?fG° , ?fS and ?fH°) of stromeyerite (Ag0.9Cu1.1S) in equilibrium with Cu2-xS and CuS have been determined. The obtained experimental values have been compared with the available literature values. New experimentally determined thermodynamic properties of the solid solution (Ag,Cu)2Sss were determined.IntroductionDue to intense mining of high grade sulfide ore minerals in the past, recently, the available sulfide ores are poor in metals and becoming increasingly complex; such that, the production of high grade metals by the conventional pyrometallurgical processes is compromised. Consequently, smelters are in need to modify their operating flow sheets and strategies for processing more complex feed materials economically, while meeting the strict environmental regulations. To make the appropriate modifications, accurate thermochemical data of phases and phase assemblages which exist in these complex ore minerals are essential.Silver-bearing sulfosalts are encountered in ore minerals for the production of base metals and are common sources of silver. Among the silver-based sulfosalts, stromeyerite (Ag0_9Cu1.1S) is relatively common ore mineral in most hydrothermal vein and replacement deposits [1]. Recently, the ternary chalcogenide compound Ago0.93Cu1,07S has been studied, intensively, due to its high ionic conductivity and gradual disorder in the sequential phase transitions [2]. Therefore, accurate knowledge of the thermodynamic properties of stromeyerite has considerable fundamental and practical interest in many aspects of extractive, chemical and physical metallurgy."

Jan 1, 2014

By Jing-she Li, Hai-yan Tang, Cheng-song Liu, Wei Liu

"In order to effectively utilize cheap and low quality iron ores, a hematite ore in a certain steel plant in Xinjiang was researched on to obtain ""iron increase and silicon reduction"" by ore dressing operation experiment and the performance indexes of the hematite ore were optimized. Based on the fundamental characteristics and high-temperature properties of the concentrate after ore dressing and other five kinds of iron ores which were co=only used in this steel plant, ore matching principles were proposed and a sintering ore blending optimization model was established. Finally, sinter pot test was carried out to verify the validity and practicability of the sintering ore blending optimization model which was aimed at giving consideration to the sintering indexes and the cost.IntroductionIn recent years, the price of imported iron ore with high quality is always at a high level, while iron ore self-sufficient rate in China is less than 50%. Enormous market demand and high dependence of domestic enterprises on imported iron ore makes the price of it hardly return to rational. In order to get rid of the situation of long-term meager profit and even deficit, more and more iron and steel enterprises in China transit their focus of reducing production cost to the utilization and development of relatively cheap but low-grade iron ore resources at home[l-4l_ However, besides the disadvantages of low iron grade, high content of impurities and complex embedded properties, the high-temperature properties of iron ore often go beyond the suitable ranges for producing sinter with high quality. Thus directly utilization of this kind of iron ore without ore dressing process would probably affect the metallurgical performance and indexes of sinter ore.Previous research and production practice have shown that traditional iron ore matching in sintering mainly focus on the reasonable collocation of properties of iron ores with low quality and high quality, but pay less attention to ore dressing process of low quality iron ores and matching them with high quality iron ores. Actually, compare with directly utilization, iron ores with low quality after ore dressing have higher suitability for matching with high quality ones which is beneficial to reduce the consumption of iron ores with high quality and control the production cost of sintering [5-s1."

Jan 1, 2014

By Zhao Guangwen, Wu Tan, Qiuzhan Tian, Duan Shuzhen

"A thorough study of lost currents in bipolar cells has been made for the development of the great potential of bipolar cells in energy saving. A proper equivalent circuit for bipolar cells has been found, and mathematic methods for computing lost currents at all kinds of polarization have been developed.At linear polarization, the lost currents can be computed by solving either a tridiagonal matrix or an ordinary differential equation of second order. This kind of values can be used to evaluate the minimal lost currents at given conditions. At other kinds of polarization, the lost currents can be computed by the same methods as above if the necessary experiments of measuring the cell voltages of every electrolytic compartment have been made. This kind of values can be used to design bipolar cells at practical conditions.Extensive experiments have been made to evaluate the effects of electrode polarization, emf of galvanic cell for the formation of electrolyzed substance, gaseous products, geometric dimensions of electrolytic cells, special resistance of electrolyte used, and the total and ordinal number of electrolytic compartments on lost currents. It is the first time to make such a systematic research by experiments in the world. Experiments showed that theoretic models were in good agreement with measured data. Experiments also showed that D.C. energy consumption of 0.45 kwh/kg of Pb for lead electrolysis from molten chlorides could be achieved in a cell with 7 bipolar electrodes.IntroductionIt is very promising to apply bipolar electrolytic cells to electrolysis of aluminum, magnesium, lead, zinc and perchlorinates for their great potential of energy saving for example, bipolar cells had been used in the production of magnesium and saved more than 30% of energy, being one of the three main techniques of energy saving in the production of titanium sponge (1)."

Jan 1, 1988

By J. Wong

We report a successful use of x-ray absorption spectroscopy to probe the chemical and structural environment of trace elements in coal. When applied to vanadium in coal, it was found that vanadium exists in at least two environments: a trivalent site 6-fold coordinated by oxygens at ca. 2.0~ and a tetravalent site 5-or 6-fold coordinated also by oxygens, one of which forms a short V=O bond at ca. 1.6a. No evidence of nitrogen (porphyrin)1'or sulfide environment was found. It was also found that the vanadium environ-ments in the raw coal did not survive unchanged in a liquefaction process. These findings have implications for coal cleaning processes and for trace element release into liquefaction process streams.

Jan 1, 1982

By A. E. M. Warner

In co Limited has long and extensive experience in converting nickel-copper primary smelting mattes over a broad range of nickel/copper weight ratios and combined nickel-copper-cobalt contents. At the Copper Cliff Smelter, the composition of the converter product matte has to meet the requirements of the matte separation process; at the Thompson Smelter, converter matte of a different composition is cast into anodes for nickel electrorefining; and in Soroako, Indonesia, a very low copper product matte is granulated for the Japanese market. Recently, Inco has conducted pilot plant testing of three possible nickel-copper matte continuous converting routes, namely flash converting, oxygen top blowing-nitrogen bottom stirring, and tuyere blowing. This test work has generated substantial new information on nickel-copper matte converting chemistry. This overview paper reviews the metallurgy of nickel-copper matte converting, in particular the behaviour of cobalt and the operating conditions required to meet the iron and sulfur specifications of the product matte. The relevant thermodynamic information is used to discuss the industrial data.

Jan 1, 2003

By Zbigniew Zurecki

The selection of atmosphere composition is critical for controlling surface quality of reactive aluminum alloys during solution treatments. An improper selection of annealing atmosphere can result in surface blistering in AI-Mg and sub-surface depletion of lithium in AI-U ingots. To determine optimum atmosphere compositions for homogenizing A1-Mg and Al-Li alloys, Ii number of exploratory experiments were carried out in air, nitrogen, and carbon dioxide based atmospheres including reactive impurities or additive such as moisture and sulfur hexafluoride. This paper describes the influence of these atmospheres on high-temperature oxidation and sub-surface defects. The results are discussed in terms of the change in Pilling-Bedworth ratio.

Jan 1, 1996