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By Helena Byrdziak

Polish Copper Industry, located in the Lepica-Glogów region and operated since the 1970's, includes four mines and two smelters, "Legnica" and "Glogów", the latter consisting of "Glogów" I" and "Glogów II" both having different technologies. The "Legnica" and the "Glogów I" smelters using shaft furnaces, so sulfur elimination largely takes place during batchwise converting, resulting in fluctuation SO2-concentration between less than 1% up to 10% in the converter pas W the sulfuric acid plants. The ensuing difficulties of the past have now largely been overcome. Introduction of flash smelting at "Glogów II" with subsequent acid making by double SO2-conversion from the stable process gas, contributed significantly to further reduction Of SO2-emission. In 1994 a new double conversion sulfuric acid plant was installed at "Glogów l" as well as a "Solinox" desulfurisation plant at "Legnica", further reducing SO2 emission considerably, The next step towards this goal under consideration is a semi-dry desulfurization system for the "Glogów I" power station, SO2- abatement measures by KGHM and the results thereby achieved are presented.

Jan 1, 1996

By Jin Yu, Fang-Qiu Zu, Yun Xi, Li-Na Mao

"According to the behaviors of resistivity-temperature of Cu-Sb70 melt, which suggests a partly reversible temperature-induced liquid structure transitions (LST) could occur in this alloy, in this paper, we investigated the dependence of solidification on the liquid state. Both resistivity and temperature were measured to track solidification process. The results show that the nucleating undercooling of the melt which experienced the LST increased and the solidified time decreased. Meanwhile, the solidified microstructures refined evidently, with the microscopic pattern of primary phase changes from disordered pillarlike dendrites into homotaxic ones. Moreover, it is verified that the microstructures would be different if the reversible part of the LST was restrained. The new phenomena and results reflected in this paper suggest that grasping the rules of melt structure change with temperature before material processing will give help for controlling the solidification more effectively and finally resulting in more ideal microstructures.IntroductionThe structure and quality of liquid alloys have a direct and important influence on the structure, performance and quality of the solidified ones. In recent years with in-depth study of liquid structure, researchers have found that some liquid structure transitions (LST) could occur on dependence of the temperature or pressure [1-5]. And the article [6] reported that a pressure-induced reversible LST was found in liquid triphenyl phosphite, which further confirmed the authenticity of the existence of the LST. Furthermore, in our earlier studies of Sn-based melts using resistivity method, some abnormal structure changes induced by temperature have been found at hundreds of degrees above liqiudus, and these LSTs are partly reversible[7]. This phenomenon has been discussed and it is suggested that the reversible LST in Sn-based melts are related to the short-range ordering (SRO) structures of Sn, which are tetrahedron structure with covalent bonding. However, does this reversible LST exist in other melts too?"

Jan 1, 2012

By M. Rosales

By a physical and mathematical modeling, the behavior of the tri-dimensional waving, and the movement of the gases at the Teniente Converter was studied. The mathematical model considers the condensed phases of white metal and slag, along the gas phase, and includes the k-e model for the turbulence description. Both the physical model and the mathematical model allow to conclude that from a fluidynamic stand point the Teniente Converter clearly can melt 3000 tpd of concentrates. Also, both models are suitable to predict the slag fluidynamics and its spacial distribution inside the Teniente Converter, and the splashing in the tuyere zone as well.

Jan 1, 2006

By Jiao Li, WenhuiMa, KuixianWei, YongnianDai, Cong Zhang

The paper studied the diffusion process of nitrogen and characteristic distribution of iron impurities in the bottom of cast crystalline silicon ingot along the direction of crystal growth. According to the dynamics analysis of the decomposition of Si3N4 coating, the diffusion process of nitrogen into multicrystalline silicon ingot during casting process should be divided into three steps. The diffusion length of nitrogen in multicrystalline silicon ingot is 700 μm. The results of EDS analysis indicate that the distribution characteristic of iron in multicrystalline silicon ingot is concerned with the diffusion process of nitrogen in this length. Based on the above research results, the distribution model of iron in casting multicrystalline silicon ingot was established and verified by the experimental results.

Jan 1, 2015

By Roderick 1. L. Guthrie, Mei Li

"A mathematical model was developed to study the role of orifice shape in the detection of inclusions in LiMCA (Liquid Metal .cleanliness Analyzer) system. The fluid flow field within the ESZ was obtained by solving the Navier-Stokes equations. The trajectories of entrained particles were calculated using the equations for motion of particles. A numerical study of the effect of orifice shape on signal shape generated by inclusions passing through orifice showed that the signals in a parabolic orifice are gaussian in shape, while those in a cylindrical orifice are trapezoidal in shape. This signal shape difference needs to be taken into account when performing particle discrimination. Orifice shape influences also pass-through fraction of inclusions. Finally, a study of the orifice shape on critical conditioning currents suggested that as the polynominal coefficient of the parabolic orifice increases, the critical conditioning current, which is also the maximum operating current, decreases dramatically. These critical conditioning currents also increase as the fluid flow velocity within the ESZ increases. IntroductionThe presence of non-metallic inclusions in metals often leads to impaired mechanical properties such as a reduction in fatigue strength, and to processing problems such as tear-offs in deep drawing and increased breakage rates in wire drawing operations. Similarly, inclusions cause a variety of surface defects in rolled or extruded products.Prior to the development of the LiMCA system (1) at McGill University in the early 1980's, it was not possible to measure inclusions, in situ, in liquid metals. Compared with other techniques, such as sedimentation, filtration and metallography, which require considerable amounts of labor and time, the LiMCA method has the advantage of providing not only information on the volume concentration of inclusions, but also on the size distribution of inclusions immediately and quantitatively."

Jan 1, 2001

By Youngkook Lee

The precipitation kinetics of NbC in ferrite matrix of the Nb microalloyed steel was investigated experimentally and numerically. The mole fractions of NbC precipitates formed at different isothermal temperatures were measured as a function of holding time by electrical resistivity test and were compared with both a mathematical model based on time-dependent nucleation and growth rates and the hardness. There is a good match among the calculated and measured precipitation kinetics of NbC and the hardness. The isothermal precipitation-temperature-time diagram of NbC in ferrite matrix of the Nb microalloyed steel was newly generated. Keywords: Precipitation, Carbide, Ferrite, Nucleation, Growth, etc

Jan 1, 2003

By Heikki K. Jalkanen

Thermodynamic properties of copper-iron mattes and slag-matte distribution of copper and some minor matte constituents (Ni, Co, Mo, As, Sb and Bi) are discussed on? the basis of equilibrium measurements: a change from. oxidic to sulfidic solubility as the predominant form of dissolution of copper takes place as matte grade decreases. Distribution coefficients of minor matte constituents are complex functions of sulfur and/or oxygen potentials?. The distribution behaviour of different? metals can be qualitatively derived from their affinities to copper and stabilities. of their sulfides and oxides. The equilibrium results are compared with commercially observed values. from Outokumpu.Oy flash smelting furnace.

Jan 1, 1983

By S. J. Gerdemann

The U.S. Bureau of Mines is studying the kinetics of wet oxidation of sphalerite concen- trate (ZnS) as a possible process for a gravity-pressurized reactor (GPR). At tempera- tures in excess of 200' C, a sphalerite water slurry will react with 0, to form zinc sul- fate (ZnSO,). However, the pressure required to keep the water from boiling at these temperatures has kept this reaction from becoming a viable continuous process. The GPR can easily obtain the high pressures required for this reaction. The reaction rate is complicated by the solubility of 0, in water and the further oxidation of ZnSO, to insoluble zinc oxysulfate (Zn4(OH),S04.4H20). The effects of pressure, temperature, and particle size on the rate of reaction were investigated. Reaction rate was found to be limited by the amount of oxygen in solution. However, at 250" C and 1500 psia, over 90 pct of the zinc was solubilized in less than an hour. The conditions for maxi- mizing the Zn++ in solution, while minimizing oxysulfate formation, are discussed.

Jan 1, 1993

By Katsutoshi Inoue, Shafiq Alam

Several novel types of chemically modified chitosan were prepared by immobilizing functional groups of EDTA and DTPA onto polymer matrices of chitosan in order to investigate their potential for mutual adsorptive separation among rare earths. Following the batch wise adsorption tests to elucidate their basic adsorption characteristics for rare earths, mutual separation was carried out using a column packed with the chemically modified chitosan. The separation between Sm(III) and Y(III) was tested using a column packed with EDTA-type chitosan while mutual separation among 4 light rare earths, La(III), Ce(III), Pr(III) and Nd(III) was tested using a column packed with DTPA-type chitosan. In both cases, satisfactory mutual separation was achieved by the chromatographic operation using these chemically modified chitosan.

Jan 1, 2014

By Glenn Stevens

After 40 years of operation with the original design, Pan Pacific Copper determined it was necessary to rebuild the Saganoseki Flash Smelting Furnace to continue safe operation. The original design employed a rigid steel frame, which, through hearth growth, led to severe distortion of the frame. Contributing to the continued growth of the hearth were thermal cycles that occurred during the government mandated annual shutdowns. Hatch designed a unique sprung bound, pivoting binding frame to maximize crucible size within the existing furnace footprint, while integrating the PPC designed cooling jackets. The bound system maintains tight brick joints, while the new conductive hearth design with integrated bottom cooling produces a protective freeze layer to accommodate higher furnace throughput. Minimization of furnace downtime for the rebuild was achieved through effective construction planning, highly trained contractors, and through an efficient start-up and ramp-up to full production.

By E. Salinas-Rodriguez, J. Hernández-Ávila, E. O. Ávila-Dávila, A. Romero-Serrano, M. Perez-Labra, G. Juárez-López

"Single phase rubidium jarosite was synthesized by precipitation from aqueous solution. X-ray diffraction and SEM-EDS analyses showed that the synthetic rubidium jarosite formed in subspherical particles with an average particle size of about 35 µm. The chemical analysis showed an approximate composition of Rbo9432Fe3(SO4)2 1245(OH)6. The decomposition behaviour of the jarosite in terms of solution pH was thermodynamically modeled using FACTSage by constructing the potential-pH diagram at 298.15 K. The E-pH diagram showed that the decomposition of jarosite leads to goethite (FeOOH) together with Rb+ and SO42- ions. The experimental decomposition of the Rb-jarosite was carried out in alkaline solutions with five different Ca(OH)2 concentrations. The decomposition process showed an ""induction period"" followed y a progressive conversion period where the Rb+ and SO42- ions formed in the aqueous solution. In contrast, calcium was incorporated in the solid residue and iron was transformed into amorphous ferrihydrite. The kinetic analysis showed that this process can be represented by the unreacted-core chemically controlled model. The reaction order with respect to Ca(OH)2 is 0.4342 and the calculated activation energy is 98.70 kJ mol-1. IntroductionJarosite type compounds are hydrous sulfate minerals containing alkalis and ferric ions, MFe3(SO4)2(OH)6, where M can be H3O+· Na+, K+, Rb+, Ag+, NH4 +, Tl+, ½ Pb2+ or ½ Hg2+. Jarosite-type compounds were formed by the natural ""in situ"" oxidation of pyritic ores leading to the replacement of the original iron sulfides and iron oxides (Dutrizac and Kaiman) [1]. The great interest in jarosites is due to its ability to eliminate or diminish the iron concentration of the acid leach solutions produced in the hydrometallurgical zinc process, with relatively low losses of divalent metals such as Zn2+, Cd2+, Cu2+ or Co . However, the losses of the metal values demand a careful study of the conditions under which the jarosite compounds are formed together with their chemical properties."

Jan 1, 2012

"Injection technology has been an important subject from the early days of ladle metallurgy until the present. During the last decade, there have not been many publications in the area of injection technology. It is the author's opinion that with the challenge to find new solutions especially to environmental and energy related problems as well as better understanding of phenomenas from computer modelling, a new era of inventive injection technology developments is at hand. This is illustrated in the article with examples from six different areas where MEFOS is or have recently carried out R&D work related to issues from the injection technology field. IntroductionThe boom in injection technologies came with the introduction of ladle metallurgy treatment during the '70s and '80s. Since then, the theories and principles have been thoroughly laid down by a number of scientists and also published at several early SCANINJECT conferences.Not many new technologies/applications have been presented during the last ten years. This might lead one to believe that everything is known and done. Those, like MEFOS, who are challenged to find technological solutions to a number of environmental problems and energy saving issues in the pyrometallurgical field are, however, continuously faced with the task of developing new injection technologies.Especially, the call for sustainable technologies to solve environmental problems is a challenge for metallurgists all over the world and it will surely induce a revival of injection technologies. So, in order to encourage all injection experts, let us share some new experiences and let us encourage each other's creativity to solve some of the demands of the future society.The following show some examples of technologies under development, or recently tested."

Jan 1, 1996

By Takashi Araki

In this work, we have elucidated the two-step oxidative reaction mechanism of 2,4,5-trichlorophenol by adsorbing oxygen atom for oxidative decomposition reaction of 2,4,5-trichlorophenol on oxide catalyst surface using ab initio molecular orbital calculation. In the first oxidation, total energies of reaction products have been shown extremely stabilized at all oxidation positions. This reaction occurs due to charge transfer from benzene ring to adsorbing oxygen atom. As a result, ? bonding of benzene ring are weakened. However, the benzene ring of 2,4,5-trichlorophenol does not perform cleavage reaction. In the second oxidation, the benzene ring of 2,4,5-trichlorophenol can perform cleavage reaction, since the second oxidation obtains larger stabilized energies than the first oxidation.

Jan 1, 2003

By Takashi Araki

In this work, we have elucidated the two-step oxidative reaction mechanism of 2,4,5-trichlorophenol by adsorbing oxygen atom for oxidative decomposition reaction of 2,4,5-trichlorophenol on oxide catalyst surface using ab initio molecular orbital calculation. In the first oxidation, total energies of reaction products have been shown extremely stabilized at all oxidation positions. This reaction occurs due to charge transfer from benzene ring to adsorbing oxygen atom. As a result, 1£ bonding of benzene ring are weakened. However, the benzene ring of 2,4,5-trichlorophenol does not perform cleavage reaction. In the second oxidation, the benzene ring of2,4,5-trichlorophenol can perform cleavage reaction, since the second oxidation obtains larger stabilized energies than the first oxidation.

Jan 1, 2003

By H. Y. Sohn, Haitao Wang, Moo Eob Choi

"A novel ironmaking technology is under development at the University of Utah. This technology produces iron directly from iron ore concentrate by gas-solid suspension reduction. Hydrogen is the main reducing agent for high reactivity and for the elimination of carbon dioxide release in this ironmaking process. The direct use of concentrates allows bypassing the problematic pelletization/sintering and cokemaking steps in the steel industry.Intrinsic kinetics of the suspension reduction of magnetite concentrate particles by hydrogen has been measured. Experiments were carried out in the temperature range of 1423-1673 K, other experimental variable being hydrogen partial pressure, the amount of excess hydrogen and particle size. Under most experimental conditions, 95% reduction was attained within several seconds, which presents sufficiently rapid kinetics for a suspension reduction process. The reaction kinetics followed the nucleation-and-growth equation, and a rate equation that contains all the effects of the experimental parameters has been obtained.IntroductionWith the rapid increase in steel production, it is critical to control CO2 emissions which is the main greenhouse gas. It is inevitable to release a huge amount of CO2 when coke and/or coal are used as the main reducing agent in producing iron. As one of the methods to reduce the CO2 emission from ironmaking, the utilization of the gaseous reducing agents and fuels, including hydrogen, has been investigated [1-6]. The use of such gases forms the basis for a new ironmaking technology under development for producing iron directly from fine concentrates by a gas-solid suspension technology. This technology would reduce energy consumption by about 40% of the amount required by the blast furnace and drastically lower environmental pollution, especially CO2 emission, from the steel industry [4]. This is accomplished by adopting H2-based reductant and bypassing pelletization/sintering and cokemaking steps. Unlike other gas-based alternative ironmaking processes using shaft furnaces or fluidized-bed reactors, the suspension reduction technology is a high-intensity process because it will not suffer from the problems that other processes do when operated at high temperatures mainly from the sticking and fusion of particles."

Jan 1, 2011

By Rashmi Kumar, Amit Chatterjee, Sanjay Chandra

The practice of adding alloying materials to a molten bath is an integral feature of many pyrometallurgical operations. However, very little is known about the dissolution rate and solution mechanisms of solid additives in liquid melts. In foundries where large tonnages of liquid metals are handled, there is considerable interest in achieving optimum metal quality at minimum cost. This objective is influenced by several factors and the solution is often plant specific. Though the amount, sequence and mode of ferroalloy addition vary from plant to plant, various fundamental factors determine how quickly these additions dissolve in the bath. At the Ingot Mould Foundry (IMF) in TATA STEEL blast furnace hot metal is used to cast ingot moulds. The composition of hot metal desired for making ingot moulds demands addition of 20 kg each of Ferromanganese and Ferrosilicon in the 12 T transfer ladles into which the blast furnace metal is poured at the IMF. Owing to low temperature of hot metal at the IMF, casting commences immediately and complete dissolution of the ferroalloys is often not possible. To study this aspect in detail and to evolve suitable corrective measures, a mathematical model for the melting of a solid particle in a liquid metal bath was developed at TATA STEEL. The model was validated using the data available in literature. In keeping with published work, two separate dissolution periods were identified - a "shell period" and a "free dissolution period". The maximum thickness of the crust formed around a spherical particle shortly after immersion, can be obtained by using the mathematical model which has been developed. The model can also be used to investigate the effect of various parameters such as superheat of the bath, size of the particle, etc., on the maximum crust thickness and the particle melting time. On the basis of this study, the addition of ferromanganese and ferrosilicon was optimized at the IMF in Tata Steel.

Jan 1, 1996

By Yun Soon Han, Joo Hyun Park

Indium (In) solubility in the FeO-SiO2-Al2O3-5%CaO slag was measured under p(O2)=10¯¹¹ atm at 1573 K to clarify the dissolution mechanism of In in FeO-bearing metallurgical slag. The In solubility increased with increasing oxygen partial pressure, whereas it decreased by increasing the activity of basic oxide, viz. FeO. Thus, a dissolution mechanism of In in the FeO-SiO2- Al2O3-5%CaO slag was described by the following equation. In(s)+1/4O2(g)=(In+)+1/2(o2-) The enthalpy change of the In dissolution reaction was negative, indicating that the dissolution reaction was an exothermic reaction. This is consistent with the above reaction mechanism.

Jan 1, 2014

By T. Watanabe, T. Fujiwara, S-Wan Song, Y. Nakagawa, R. Teranishi, M. Yoshimura

"We have tried a new method to fabricate cobalt oxide films onto porous films directly by an electrodeposition method at low temperature. The porous substrate films (membrane-filters and paper) were placed between a LiOH solution and a CoSO4 solution and treated under electricalcurrents of ~1 mA/cm2 using carbon cathode and anode. Effects of temperatures, flow rates and electrical currents have been investigated. As a result, we found that the LiCoO2 films and Co3O4 films were successfully fabricated on paper and/or porous PTFE filters at 120 °C, while CoOOH films were deposited at 80 °C. Furthermore, LiCoO2 films did not cover whole the substrates, but was fabricated just over the anode. The chemical reactions of electrodeposition were also considered from these results.IntroductionRecent agreements on global environment require rapid progress of low energy and low waste processings for the fabrication of thin films that succeed to the mass production with the high consumption of the fossil fuels (such as physical vapor deposition°, chemical vapor deposition2), dip coating with firing3) etc.). The total energy consumption in aqueous systems should be the lowest among all these processing routes, because a much lager excess of energy is necessary to create melts, vapor, gas, or plasma than to form an aqueous solution at the same temperature4)The ""Soft Solution-Process"" (SSP) was one of the best concepts to realize the low energy and low waste fabrication of inorganic materials. 5) Generally speaking, SSP gives similar results to any other processing using fluids (such as vapor, gas plasma) and/or beam/vacuum processing. However, the total energy consumption of all these possessing routes should be the lowest in aqueous systems, because a much larger excess of energy is necessary to create melts, vapor, gas or plasma than to form an aqueous solution at the same temperature (Fig. 1). This idea can be easily demonstrated, using the simple example of BaTiO3. The energy diagram for the formation of BaTiO3 from various precursors is shown in reference 4. The driving forces (AG) for representative synthesis reaction of (1), (2), (3), (4) and(5) are 38, 727, 3685, 17 and —14kcal/mol, respectively at room temperature. 6' 7"

Jan 1, 2000

By Egil Krystad, Merete Tangstad, Kai Tang, Gabriella Trenell

"A new UMG-Si refining concept has been proposed in this paper. Liquid Si and another liquid metal phase (Me) were separated by the molten slag spontaneously based on their different physicochemical properties. Two metal/slag distribution reactions are able to occur in the system simultaneously. Experimental investigation on the B and P distribution equilibria among Si/slag/Me was carried out in the graphite resistance furnace under the inert atmosphere. The B and P doped silicon was in equilibrium with either the SiO2-CaO or SiO2-CaO-l0%CaF2 slags at 1600 and 1650°C, respectively. The pure Fe and Cu metals were used in order to ""capture"" B and P in the slag phases. B and P in samples were determined by the ICP-MS. B and P distribution coefficients for the Si/slag/Me equilibria were compared with the theoretical calculations. The possible kinetic barriers for the Si/slag/Me three-layer equilibria have been analyzed. The metal contaminations in the three-layer equilibria were also examined. The present study provides a new approach for the refining of MG-Si.IntroductionMost of the impurities in the metallurgical silicon (MG-Si) are rather ""dilute'', ranging from few to several thousand ppms. However, the target impurity levels for upgrade metallurgical silicon (UMG-Si) feedstock are often far below the level of ppm. In such extreme case, the conventional refining technologies face the great technical challenges. B removal by slagging has already been implemented industrially. Removal of Pis frequently carried out by the vacuum distillation. The separating treatments for B and P removals lead to increase refining cost, total CO2 emission and longer pay-back time of solar cell module.It is well known that the phosphate capacities of slags in equilibrium with liquid silicon are extremely lower. However, if we introduce another phase that possesses high ""phosphor capacity"" into the Si/slag system, one would expect to continuously remove P from Si through molten slag to the new ""phosphor capturer"". The so-called three-layer refming concept is thus proposed in the present study. Liquid Si and another liquid phase (Me) are separated by the molten slag spontaneously based on their different physicochemical properties. Two metal/slag distribution reactions are able to occur in the system simultaneously."

Jan 1, 2013

By W. G. Davenport

Chapters 19 and 20 examine direcHo-copper flash smelting and flash converting. This chapter compares the two processes and suggests which is likely to be 'the more economic for a given concentrate. It: (a) uses Chapter 19's direct-to-copper industrial oxygen and oil requirements (b) adds the energy required for electric furnace recovery of Cu from direct-to-copper slag (Czemecki et al 1999) (c) combines Chapter 20's, flash converting calculations with Chapter 18's flash smelting calculations to determine their combined industrial oxygen and hydrocarbon fuel requirements (d) adds the energy required to granulate, crush and dry flash smelting matte for the flash converter (e) adds the energy required to granulate and dry flash converter slag for recycle to flash smelting (f) compares direct-to-copper and flash smelting/flash converting in terms of their total equivalent hydrocarbon ener.gy requirements.

Jan 1, 2001