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By M. Nilmani, H. Pham

"A mathematical model was developed for the dissolution of particles in gas-stirred liquid baths, linking the hydrodynamic flow field of the bath, the average particle trajectory and liquid-side mass transfer controlled dissolution kinetics. The model was validated by comparison with experimental data for the dissolution rates of urea particles in gas-stirred aqueous CaCl2 solutions measured during this study. The dissolution rates of urea. particles were measured using an image analysis system.The effects of operating conditions on the dissolution rates of urea particles were investigated. It was found that the key operating parameters influencing the utilisation efficiency of particles were the gas flowrate, particle diameter and lance submergence. An optimisation of the operating conditions for the model urea-aqueous CaCl2 system indicated that the utilisation efficiency increased with decreasing gas flowrate and decreasing particle size for a given lance submergence.IntroductionThe utilisation solid reagents in molten baths varies from one process to another, depending upon the rates and mechanisms of the reactions between the particles and melts, as well as the trajectory and residence time of the particles in the melts. Previous studies have not attempted to predict the utilisation efficiency of injected solids by coupling the motion of the particle with its dissolution rate. Instead, the particles have usually been assumed to remain suspended in the bath until completely dissolved, and the mass transfer coefficients were based on the average specific mechanical energy dissipation rates in the bath. Investigations of this nature relevant to the present study have been undertaken by Apelian et al. [1], Brucato et al. [2] and Langberg and Nilmani[3]. The objective of the present study was to develop a mathematical model, incorporating both the reaction kinetics between the particles and liquid and the particle motion simultaneously, to predict the dissolution rates and times of the particles. The mathematical model was validated by comparison with experimental dissolution rates of a cold model analogue system measured using an image analysis technique, and then applied to optimise the operating conditions in the model system."

Jan 1, 1996

By Zhijing Zhang, Ramana G. Reddy

"The viscosity of molten oxides is one of the important physical properties since viscosity has a decisive influence on fluid flow. The knowledge of the viscosity of molten oxides is essential for modeling and controlling of metallurgical process. In the present study, viscosities of high basic Na2O-B2O3 and Na2O-SiO2 binary melts and viscosities of Na2O-SiO2-B2O3 ternary melts were measured as a function of temperature and composition. Experiments were carried out using rotary viscometer and graphite components. Our experimental results were compared with those in literature. Based on the current experimental data, the previously developed viscosity model was modified. The characteristic features of viscosities of these melts have been discussed. The predicted viscosity results are in excellent agreement with the present experimental data in the temperature range with molten state samples. IntroductionThe viscosity of molten oxides is one of the important physical properties since this property has a decisive influence on fluid flow, and is one of key factors to be taken into consideration in process modeling. The manufacturing operations require the viscosity of molten oxides to be within certain ranges. Although, some viscosity measurements on borosilicate systems have been carried out [1-4], the viscosity data in literature are available only for a few temperatures and cover small composition ranges. The agreement between the results of these works is not satisfactory [I-4]. Even the viscosities of binary systems Na2O-B2O 3 and Na2O-SiO2 generally are well studied, the available viscosity data in literature are only found in the composition range of O to 0.333 mole fraction ofNa2O. The aim of the present study is to provide a base with accurate experimental data for reliable model extrapolation."

Jan 1, 1999

By Åke Saudström

An EAF dust sample generated in a scrap based steel mill was treated by a combination of hydro- and pyrometallurgial techniques. The EAF dust contained mainly ferritic spinels forming solid solution phases according to the general chemical formula (MnxZnyFe1-x-y)Fe2O4 and other oxide phases such as ZuO. CaO and Ca2Fe2O5. The EAF dust was first treated by hydrochloric acid leaching at p8=3 which dissolved 63% of the zinc. The pyrometallurgical treatment of the leaching residue was studied using an induction heating system to simulate some important operations of EAF smelting of the residue in combination with steelmaking. The leaching residue was mixed with carbon powder to obtain a mixture with 52.1% ZnFe2O4 and 175% carbon. The mixture, scrap, and slag former were charged together in a crucible and heated to attain a melt temperature around 1650°C. The effects of different amounts of mixture on the zinc balance and iron recovery were examined. Based on the test results, suggestions are made for the EAF recycling procedure of the leaching residue.

Jan 1, 2003

By E. Oshilna

The Mitsubishi process has many advantages pertaining to economical and environmental matters. These advantages have led to the installations of the Mitsubishi process in constructing new smelters: The Mitsubishi process utilizes highly oxygen enriched blast air and uses a special lime slag in the C?furnace. These characteristics change the . distribution of Impurities from other processes which use P.S. converters, Recently an Increased amount of secondary materials which contain impurities Is being treated at Naoshima Smelter. In order to cope with an Increment of the Impurities load and maintain the cathode quality, many Improvements have been Implemented. This paper discusses the impurities behavior In the Mitsubishi process and describes the measures taken to treat an Increased ?amount of secondary materials:

Jan 1, 1998

By Claudio Toro, Alex Moyano, Jonkion Font, Carlos Caballero, Pedro Morales

"Codelco-Chile in the last decade has carried out industrially-oriented research as an alternative to the traditional batch-type converting process. In a first stage carried out preliminary evaluations in a rearranged Peirce Smith (PS) converter, and then an exploratory test in a “Convertidor Teniente” (Teniente converter, TC) for the Codelco-Chile Continuous Converting Process. However, the validation test for this process in the TC was delayed up to the second quarter of 2007 where the validation studies were done satisfactorily.Thus, the objective of this paper is to present the results of the campaign tests validating the Codelco-Chile Continuous Converting Process in the TC1 of the Codelco Norte smelter.The results of charging the solid or liquid matte or high grade matte (“white metal”) by Garrgun, or by mouth of the 22 m x 5 m TC1 are presented. Some features of the industrially validated process are discussed, and the pilot test results of the matte injection are also presented."

Jan 1, 2009

By R. Nilsson

In the present work, an assessment of the sulphide capacities of a number of binary and ternary slag systems have been carried out in the light of a sulphide capacity model. The model is based on the expression: {CS- exp (-A G °/R T) ? ao2 / fs2-} where AGO is the standard Gibbs energy change for the above reaction, ao2 is the activity of oxygen ions and f, is the activity coefficient of the sulphide ion in the slag. In the present model, the ratio (ao2/fs2) is optimized for the experimental data available in literature. The systems assessed are the binaries MnO-SiO2, CaO-SiO2, Al2O3-CaO, as well as the ternaries CaO-Al2O3-SiO2 and CaO-MnO-SiO2. In the case of all these systems, the experimental data available in literature were complemented by measurements carried out at the Division of Theoretical Metallurgy. The sulphide capacities of some FeO- containing binary, ternary and quaternary slags are also examined. The potentiality of the model to estimate the sulphide capacities of complex slag systems from binary and ternary data is demonstrated.

Jan 1, 1996

By Susumu Okabe, Etsuji Kimura

"The Mitsubishi Continuous Copper Smelting and Converting Process is the typical applications of injection metallurgy to nonferrous metallurgical operation, where the top blowing multiple lance system is employed for the continuous feeding of the raw materials and reaction gases into the molten bath. This results in an effective dispersion of the reactants into a strongly agitated bath. These are considered as the major advantage of the process with respect to the high production efficiency. On the other hand, however, the strong agitation may cause a considerable amount of refractory wear, and the melt splash generated by the lancing may also have negative effects on the productivity, i.e. the increase in the refractory wear, the metal loss, the heat loss, and the accretion growth, etc. Therefore, the optimization of the blowing condition as wen as furnace design is very important to achieve a stable and efficient operation, and fundamental understanding of the injection, agitation, and splashing is badly needed.In this paper, fundamental aspects of the Mitsubishi Process regarding injection, especially splashing phenomena, are discussed. The splashing on a vertical plane caused by the top blowing gas injection onto liquid surface was investigated through physical model study. As a result of the study, the splashing rate on the furnace wan was wen correlated with the physical properties of the bath materials, gas velocity, cavity shape, lance/wall distance and ceiling position. Obtained equations were compiled in a computer program and have been successfully applied to the evaluation of the furnace design. IntroductionInjection metallurgy is an application of gas/solid-in-liquid dispersing operation to the metallurgical processing, and has been widely adopted in various fields in order to improve their efficiency or productivity. The dispersed small particles of gas or solid materials in the liquid phase result in increased interface area, and injected momentum causes an agitation and enhanced heat and materiel transfer. Typical examples of injection metallurgy are LD converter for steel making, PS converter, Noranda process, Isasme1t for copper making, and Mitsubishi Material's continuous copper smelting and converting process, and so on."

Jan 1, 1996

By Jong-Ren Tarng, Gin-Hwa Chen, Wen-ku Chang, Ke-Ming Lin, Yuan-Haun Lee

"The majority of early studies used X-ray diffraction, but this requires a model to interpret the diffraction processes. A turbostratic model has been applied by Warren, Franklin and Bacon to a wide range of materials including both soft and hard carbons. Maire and Mering applied the same methods to the interpretation of the (001) lines of a series of graphitic carbons. In our case, graphitic carbons undergone high temperature and high pressure graphitization processes have been evaluated by the same methods. It were found that most technological XRD data were obtained by a Rietveld method with the least-squares refinements could be in the simplest way since the full correction technique is very laborious. The behavior of carbon materials as it proceeds through the graphitization process is characterized by changes in the measured interlayer spacings (d) a~ a function of temperature. A series of graphitic carbons including the transformation of diamond to graphite through the process under high temperature and high pressure have been evaluated. A simple calibration equation has been established. IntroductionRecently, in battery industry, carbon materials are used as cathode in lithium ion batteries. However, graphitization of those carbon materials is concerned as if lithium ion intercalated into those carbon cathode. Both high-graphitization and low-graphitization carbon materials are suitable for this kind of application.As for graphitization, the starling materials from which carbons may be prepared vary extensively from pure chemical compounds, to mixtures containing II wide range of molecular weights, such as pitches. So its graphitizing, perhaps the most notable feature of the process, is the very wide range of temperature over which the perfection increase, unlike the more common transformations of solid state materials which occur in a narrow temperature range. The variables involved in the conversion of the initial hydrocarbon to a carbon residue, which may vary widely in final perfection, are time, temperature, stress and impurity content"

Jan 1, 1996

By M. A. Gimenes

The utilization of chlorination in extractive metallurgy and advanced ceramics areas has been widely investigated as a preparative route in order to obtain intermetallic compounds, which are used as precursors in the development of new materials and process. The major processes of decomposition of rare-earth ores use sulfuric acid and sodium hydroxide at high temperatures, however there is not much work concerning chlorination. In this work, a systematic study of the reaction between xenotime (REPO4), chlorine and carbon has been performed. Particular emphasis was on kinetic studies to establish optimized conditions for the reaction. The kinetics of chlorination of xenotime raw material by rare-earth elements/compounds has been studied over a temperature range from 600°C to 950°C. The influence on the rate of conversion of xenotime to RECl3 on temperature, partial pressure of chlorine, carbon content, and particle size were investigated. A global rate equation that includes these parameters has been developed. The results show that the process follows the unreacted core-shrinking model with a formation of a porous product layer. The powder X ray-diffraction technique corroborated this model showing clearly the patterns related to the formation of yttrium oxychloride (YOCl), indicating that the reaction mechanism involves the presence ofan intermediate step before the formation of lanthanide chloride.

Jan 1, 2000

By W. R. McDonald

The U.S. Bureau of Mines investigated treatment of gold and silver refractory ores and concentrates that respond poorly to conventional cyanidation techniques due to the complex mineralogy of the ore. Three types of ores were investigated: gold locked placer sands, gold locked in sulfides, and gold that is robbed from the pregnant cyanide solutions by minerals in the ore. Ore treatment included grinding, flotation, cyanidation, air oxidation, pressure oxidation, hypochlorite oxidation, roasting, and carbon in leach.

Jan 1, 1991

By V. D. Tathavadkar

Chromite ore is of immense importance for the extraction of metallic chromium and chromium chemicals. The mineralogy and crystal structure of chromite phase are therefore important part of our investigation on the extraction chemistry of chromium species. In this investigation, we have studied the effect of the processing parameters, i.e., the temperature and the oxygen potential on the microstructure and composition of mineral phases formed in the Cr2O3 ?Al2O3 -FexOy -MgO system. In particular the importance of the spinodal decomposition reaction is emphasized in the extraction of chromium as sodium chromite and sodium chromate. Experiments were carried out in order to study the differences in the crystallography of different chromite minerals. Phase equilibria in natural chromite minerals were investigated by calcining chromite mineral in air, argon, and 5% hydrogen + argon atmospheres over a temperature range from 200 to 1200 °C. The effect of the oxygen partial pressure and temperature on the phase constituents of the calcined product has been discussed. The microstructural changes were examined using scanning electron microscope (SEM) and the changes in elemental composition in different phases were analysed by electron probe micro analyser (EPMA). The results obtained from EPMA studies were used to calculate lattice parameter of the spinel lattice, and these values were compared with the values obtained from X-Ray powder diffraction data. On the basis of the experimental data, the mechanism of the spinodal decomposition of complex spinel phases is described under the influence of oxygen partial pressure and temperature.

Jan 1, 2000

By C. Burton Clark

The important role of the petrographic microscope in the petrology of refractories is discussed, based on 45 years of industrial experience by the author. Highlights of his career are used to illustrate improvements in equipment and techniques during the period. Two specific investigations are described which emphasize the interrelated use of the petrographic microscope with other instruments such as the x-ray diffractometer and scanning electron microscope. Emphasis is placed on the use of phase equilibrium diagrams for guidance in predicting and interpreting reactions that occur under non-equilibrium conditions in the manufacture and use of refractories.

Jan 1, 1982

By H. Soto, J. Jara, F. Nava

A method has been developed to recover cyanide and copper from solutions containing copper complexes and thiocyanate. Copper is precipitated as copper thiocyanate or as copper cyanide depending on pH and the concentrations of thiocyanate and cyanide in the effluent. The copper precipitate assays over 50% copper and presents good dewatering characteristics. After settling it can be separated from the effluent by filtration. The solution containing the bulk of the cyanide is then oxidized with ozone to transform the remaining thiocyanate into cyanide. This results in a regenerated solution rich in free cyanide that can be recycled to the cyanidation process. Careful control of the pH of the solution is required. First, pH of the effluent is lowered to optimize the precipitation and oxidation stages, then the pH is restored to an alkaline value to regenerate the cyanide solution. Recoveries of over 96% copper and cyanide were obtained in laboratory tests using industrial solutions. With this procedure, cyanocidic gold/copper ores could be treated economically by heap leaching, since the cyanide consumed by the copper impurities could be regenerated at very low cost (most of the cost of cyanide regeneration would be compensated by the copper credits). In order to achieve this, a bleed of the barren solution could be treated by the proposed method, and then recycled to the leaching step. The volume of solution to be treated should be large enough to keep a cyanide/copper molar ratio higher than 3:1. This would assure that copper does not cause undue interferences in the leaching or the carbon adsorption stages. If the thiocyanate content is low, the oxidation stage can be avoided, and the solution can be recycled to the leaching stage directly after the solid-liquid separation stage.

Jan 1, 1997

By S. R. Reddy

Thennodynamic properties of several quaternary systems are calculated using our recently modified Margules equations. The modified Margules equations are expressed up to infinite order in the vicinity of solvent. Quaternary system of one solvent and three,solute partials are derived. First order interaction coefficients of binary, ternary and cross -interaction parameters of quaternary system are used to'evaluate the partial functions. In the original fonn of Margules equations,derived partial functions are convergent and same 'as Unified ,Interaction Parameter Fonnalism. But considering up to infinite order of the Margules coefficients, the functions are divergent, in order to overcome this restriction, Margules equations are modified to get consistent equations. Derived partial functions are thennodynamica Hy consistent with Maxwell and Gibbs Duhem relations. The derived logarithmic activity coefficient of the solvent and solutes are consistent with the ternary systems. The calculated data, ie., activity coefficient values of nitrogen and interaction coefficients are in good agreement with the data of Fe-Cr-V -N. Fe-Ni-V -N, Fe-Cr-Ta-N and Fe-Ni-Ta-N systems.

Jan 1, 1999

By Keiji Toyabe

Several purifying techniques have been developed for controlling the impurity levels in the copper electrolyte at Niihama Copper Refinery. These have been carried out as follows; i ) the study of the reaction in liberation made it possible to raise the current efficiency for arsenic removal by more than 50% and to decrease generation of arsine sharply. By applying this method, a good performance was attained at commercial operation. li) the antimony in the electrolyte can be successfully removed by contacting it with activated carbon. This procedure is applicable particularly when there is a large amount of antimony in the copper anode. lli) for the nickel sulphate recovery from the electrolyte, an electric evaporating system was developed. The characteristics of this process are, capability of continuous operation with less manpower, the high recovery ratio of nickel sulphate (more than 85% as nickel) and no black acid formation in the treated solution.

Jan 1, 1987

By J. D. Budai, D. H. Lowndes, D. P. Norton, D. K. Christen, B. C. Chakoumakos, J. R. Thompson, B. C. Sales

"Artificially-layered structures, consisting of (Sr,Ba,Ca)CuO2 layers in the tetragonal, ""infinite layer"" crystal structure, have been grown by pulsed-laser deposition. Superlattice chemical modulation is observed for structures with SrCuO2 and (Sr,Ca)CuO2 layers as thin as a single unit cell (~3.4 Å). In addition, novel thin film superconductors were formed by using the constraint of epitaxy to stabilize SrCuO2/BaCuO2 superlattices in the infinite layer structure. Using this approach, two new structural families, Ba2Srn-1CUn+l O2n+2+ d) and Ba4Srn-1CUn+3O2n+6+ d, have been synthesized which superconduct at temperatures as high as 70 K. These results represent not only the synthesis of new structural families of superconductors, but also demonstrate that pulsed-laser deposition and epitaxial stabilization can be effectively used to engineer artificially-layered thin-film materials.Advances in the understanding of epitaxial thin-film growth of the cuprates have heightened interest in creating artificially layered superconductors.(1-3) The layered structure of the copper oxide superconductors opens the possibility of forming novel materials by carefully controlling the epitaxial growth of sub-units of the crystal structures. Thin-film growth methods offer unique opportunities for the atomic engineering of new high-temperature superconducting (HTSc) materials through the ability to form artificially layered crystal structures.(4,S) Moreover, the surfaces of single-crystal substrates provide an ""atomic template"" that can be used to stabilize epitaxial films in metastable crystal structures.An important development in forming new HTSc compounds by artificially-layered epitaxy has been the epitaxial growth of (Sr,Ca)CuO2 films in the so-called infinite layer structure.(6-17) This material, which can be considered the parent compound of all of the copper oxide superconductors, has a relatively simple, layered structure consisting of CUO2 planes separated by planes of alkaline earth elements.(18) Bulk synthesis of (Sr,Ca)CuO2 with the tetragonal, infinite layer structure generally requires the use of high pressure and high temperature bulk processing techniques.(19-24) However, recent experiments show that this metastable compound can be epitaxially stabilized at less than atmospheric pressure, resulting in the growth of tetragonal (Sr,Ca)CuO2 single crystal thin films of the infinite layer defect perovskite structure by pulsed-laser deposition (PLD) over a wide range of growth conditions.(6-17)"

Jan 1, 1994

By Takao Yasugi

The majority of copper in the raw material migrates to the de-copperized dross that forms when the crude lead produced in the blast furnace is treated in the de-copperizing process. The de-copperized dross is treated in the electric furnace producing matte, speiss, and crude lead. The de-copperized dross also contains the silver. Therefore, it is important to improve the rate of silver migration to the crude lead. For this reason, the behavior of silver between the matte, speiss and crude lead phases was examined. At the same time, several tests to improve the percentage of silver migrating to crude lead were conducted.

Jan 1, 2003

By Takahiko Okura

Most non-ferrous raw materials are associated with sulphur. To extract the metals, the sulphur is recovered typically as Sulphuric acid or liquid S02. On the other hand, natural gas may contain over 20% of hydrogen sulphide (H2S) and a huge quantity of elemental sulphur is produced through oil and gas refining processes in the world. A large fraction of the sulphur mined from natural sources is eventually returned to the earth as fertilizers, by-products of desulphurisation and neutralisation processes, or as fugitives to the atmosphere. However, the supply and demand for sulphur are in imbalance. Such situation urges to develop a new smelting process without sulphuric acid production. This paper briefly reviews the global sulphur balance and the technologies for recovering elemental sulphur. The core of this paper is a proposal to convert S02 gas to elemental sulphur by using organic materials. Some results of thermodynamic calculations and experiments are presented.

Jan 1, 2003

By R. E. Moore

The lining systems currently in use in BOF furnaces, certain steel ladles, and the slag line of electric are furnaces were developed during the late seventies through the mid-eighties using a trial and error method of combining aggregate, carbon sources, additives and binders. They are currently based on magnesia, graphite, metal additives and resin binders, the selections of each being tied to the anticipated intensity of the use conditions. The general functions of the respective constituents are well appreciated, however, there is still a great deal that is not known about how the socalled antioxidants protect the graphite nor how impurities from the graphite and the aggregate enter into the wear processes. In a simplified assessment of wear processes, it appears that if the deoxidized layer can be kept very thin, less than 810 mm in depth, and if the viscosity and quantity of the matrix glassy phases can be controlled to resist erosion of the deoxidized layer, lining life can be maximized for the various applications. This paper will discuss the characteristics of the starting materials systems currently being employed for applications requiring a deoxidation function to realize extended wear. It will not attempt to explain all the complex interrelationships between the respective constituents but will point to the potential for improvements through the use of improved constituents.

Jan 1, 1991

By Junzo Hino

Most of the waste that contains a small portion of copper is landfilled. The recycling process of copper from the waste, such as shredder residue, should be developed in order to save mineral resources and prevent environmental pollution. Shredder residue, generated from disposed automobiles and electric appliances, consists of many types of plastics, glasses and metals. The combustion heat of plastics is efficiently used for smelting in the recycling process that consists of melting and reduction. Because the waste contains numerous components the knowledge of the distribution behaviors of the main components is necessary to develop the recycling process. The distribution behaviors in the recycling process are evaluated by using the thermodynamic calculation program, HSC Chemistry. The calculation results are compared with the practical operation data of the recycling process and discussed.

Jan 1, 2003