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By Dian Adisty, Leiv Kolbeinsen, Eli Ringdalen

In Si and FeSi production, the main Si source is SiO2, in the form of quartz. Reactions with SiO2 generate SiO-gas that further reacts with SiC to Si. During heating, quartz will transform to other SiO2 modifications with cristobalite as the stable high temperature phase. Transformation to cristobalite has been investigated and shown to be a slow process where the rate varies between the investigated quartz types. The effect of quartz versus cristobalite as SiO2 source has been studied for reaction (1) 2SiO2 + SiC = 3SiO + CO, by heating of pellets with SiO2 + SiC in Ar-gas. The reaction was faster with cristobalite than with quartz. Initial experiments indicates that this is the case only in Ar and not in CO-atmosphere The higher specific surface area of cristobalite is believed to contribute to the higher rate. The industrial consequences of the observed difference between quartz types are discussed.

Jan 1, 2014

By M. S. Moats

Galvanic stripping, in conjunction with solvent extraction, has been proposed as a technical option to the challenging problem of iron removal in certain hydrometallurgical processes. The galvanic stripping process is based on the ability of a solid metal to directly reduce ferric ion to the ferrous state in an organic media. Stripping the iron into the aqueous phase is then easily accomplished. Previous work has shown the reaction kinetics and efficiency are affected by such operating parameters as water and oxygen contents, temperature, time and metal reductant. In this study, the optimum operating range for some of these variables was determined. Both zinc and iron metal were used in the separate stripping of iron from D2EHP A. Reasons for the differences in the extent of the reaction obtained using the various conditions are discussed.

Jan 1, 1996

By Brian Balmforth

Solvent extraction has been applied successfully to the recovery of a range of metals from a variety of process streams. Particular benefits are derived from the use of new highly selective extractants. These will be exemplified by case studies including the recovery of zinc from sulfate and chloride media using ZENECA's new extractants which show a very high selectivity over iron and the recovery of antimony and bismuth from copper refinery electrolytes using ZENECA's strong and selective extractant DS5834. The conclusions are drawn that solvent extraction is a cost effective technology for metal recovery and recycling, even when used to treat relatively small volume/low concentration process streams, and that it can provide the essential enabling components of a larger system for waste minimisation programmes.

Jan 1, 1996

By G. Glinski, K. A. Pericleous

"Recent advances in new computational modelling techniques such as Lattice-Boltzmann and Dissipative Particle methods offer the prospect of simulating complex fluids such as colloidal and dense suspensions in industrial processes. They are referred to as mesoscopic methods since they lie between molecular dynamics at a microscopic atomistic scale «lO-9m) and traditional macroscopic CFD methods (> 1O-2m). The models behave like a 'coarse-grained' gas consisting of fictitious interacting particles, which are much larger than the real molecules of the actual fluid they represent. Inter-particle forces are set so that the collisions collectively mimic the phenomenological transport properties and flow of the underlying fluid at a macroscopic scale.Much of the developmental work to date has focused on laying theoretical foundations based on thermodynamic and kinetic theory. Successful applications include predictions of macroscopic transport properties of complex fluids and flows in porous media and filters. With the constant increase in computational power, these mesoscopic methods are now sufficiently developed to determine their suitability to simulate complex fluid flows in real industrial processes. This work describes the application of meso scopic methods to the stencil printing of solder pastes in the assembly of electronic components. The aim of this work is to assess the ability of these methods to study the transport mechanisms of individual solder particles suspended in the flux solvent as they enter and fill the micro-apertures of a stencil. This paper demonstrates the coupling of such mesoscopic methods to continuum CFD methods to predict the flow of dense suspensions (i.e. solder paste) in industrial processes."

Jan 1, 2001

By D. Doungdeethaveeratana

The extraction kinetics in a novel solvent extraction process have been investigated. In this process, the liquid-liquid emulsion is generated by bottom gas injection into countercurrently flowing aqueous and organic phases. This process has a number of advantages over the mixer-settler unit or the spray column in terms of simple equipment configuration, without any mechanical moving parts, and the ease of cleaning and process control, while providing a sufficiently large interfacial area for rapid mass transfer. The overall rate increased with increasing gas injection rate and height of the aqueous phase but decreased with increasing injector diameter at the same gas injection rate. The variation of the overall rate constant was correlated against a set of dimensionless numbers, representing the operating conditions. Extraction rates and efficiencies comparable to those in a mechanically generated emulsion were attained in this new process.

Jan 1, 1998

By A. González

Arsenic is one of the main contaminants present in Chilean copper concentrates and its abatement represents a challenge for the process metallurgy, particularly under the strong environmental requirements in the global community. The possibility to form ferric arsenate directly from a gas phase by means of a heterogeneous reaction between an arsenic gas bearing and iron oxide was studied at laboratory scale. A thermodynamical analysis for the system Fe-As-O-S has been initially made, in order to obtain the stability conditions for the ferric arsenate or other FeAsyO2 type compounds. Experiments were made using an hematite sample suspended in a thermogravimetric device. AS4O6 gas generated from solid AS2O3 that was passed through the iron oxide sample and its instantaneous weight change was recorded directly. A kinetic study for the AS4O6 volatilization was made to control the gas composition. A chemical control between 300 and 600°C with an apparent activation energy of around 14 Kcal/mol As2O3 was determined. The samples after the reactions were chemically and XRD analysed. Arsenates detected corresponds to complex compounds. Results shows a dependence on temperature and oxygen content in the gas phase. The kinetics for iron arsenates formation is slow, reaching an arsenic capture of 6% after 80 minutes of reaction when an oxygen content of 50% is fed continuously at 800°C and 3,56% As in the gas. Experiences made at the same temperature but under higher oxygen content in a closed reactor, allowed arsenic capture close to 60%. For higher temperatures the capture is considerably lower.

Jan 1, 2003

By V. D. Tathavadkar

Natural chromite mineral is a solid solution of spinet end members namely: chromite (FeCr2O4), hercynite (FeA1204), magnetite (Fe3O4), magnesio-chromite (MgCr2O4), (MgA12O4), and magnesio-ferrite (MgFe2O4). A phase transformation in chromite minerals occurs in oxidising conditions during the soda-ash roasting reaction. This phase transformation plays an important role in improving the extraction efficiency of Cr3+ from mineral phase. The extraction efficiency of chromium (Cr3+) from chromite to a water¬soluble sodium chromate (Cr6+) salt depends upon the decomposition kinetics of the spinet phase. An investigation of the phase changes in chromite ores in the absence of sodium carbonate was carried out in air, argon, and in argon +5 % hydrogen gas mixture. The thermodynamics of phase transformation reaction in chromite solid solution phase is discussed using the solution model proposed by Sack and Ghiorso [1]. The microstructural changes and the changes in elemental compositions of different phases were examined by SEM and electron probe microanalysis (EPMA) respectively. The experimental results indicate that the solid solution spinet phase in chromite mineral undergoes spinodal decomposition under the influence of oxygen partial pressure and temperatures. The structure of phases formed and their morphologies suggest that the phase decomposition may be similar to those observed by Burkert et. a]. 121, although the scale of phase separation in chromite appears to be strongly dependent on oxygen partial pressure.

Jan 1, 2001

By Hee Dong Jang

Crystalline metal oxide nanoparticles such as lithium cobalt oxide (LiCoO2) and indium tin oxide (ITO) were synthesized from sprayed droplets of aqueous precursor solution by flame spray pyrolysis. Complete thermal decomposition of the aerosol precursors was obtained at high flame temperature. Molar concentrations of the precursor solution, and the flow rate of combustion gas such as hydrogen, oxygen and air were varied to control particle size, size distribution and crystal structure. The crystalline nanoparticles synthesized were nearly spherical, and their average primary particle diameters ranged from 11 to 35 nm for LiCoO2 and from 8 to 15 nm for ITO.

Jan 1, 2006

By Yuhsuke Mizukami

Crude high Cr containing steel such as tool steel, heat-resistant steel or stainless steel is produced by dissolution of high carbon ferro-chromium into molten crude steel. In the refining process, decarburization is performed at the first stage, and deoxidation is followed in the next stage. Therefore, the equilibrium relation between dissolved Cr and 0 in molten Fe-Cr alloy after decarburization is very important when yield of deoxidizer is considered for the ovemll control and optimization of the process. It is well known that the yield of deoxidizer does strongly depend on the kinds of refractories of furnace in the secondary refining process. In the present work, the equilibrium relation between dissolved Cr and O in molten Fe-Cr alloy has been measured in a Cr2O3, MgO or Al2O3 crucible at steelmaking temperature. O contents at given Fe-Cr components have been lower in order of Cr2O3, Al2O3 and MgO crucible. The present results have been discussed based on the activities of the constituents in pure solid Cr2O3, and FeO-Cr2O3, MgO Cr2O3 and (AI,Cr)2O3 solid solutions.

Jan 1, 2003

By Srinath Viswanathan, Adrian Sabau

"In general, the occurrence of microporosity during metal casting is due to the combined effects of solidification shrinkage and gas precipitation. The governing equations for fluid flow and hydrogen evolution indicate that porosity formation and fluid flow are strongly coupled. However, in most studies on microporosity, it is considered that the porosity formation does not influence the fluid flow in the mushy zone. In this study, a computational methodology is presented for the numerical simulation of interdendritic fluid flow and microporosity evolution. The solution algorithm presented includes a fully coupled, implicit treatment of microporosity and local pressure in the mushy zone. The effects of microporosity evolution due to the local pressure drop in the mushy zone, and pore expansion in casting regions where liquid feeding alone cannot compensate for the solidification shrinkage are also considered. It is shown that neglecting the effect of porosity formation on the pressure in the mushy zone yields higher pressure drops. By its growth, microporosity partially compensates for the solidification shrinkage, reducing the feeding demand. A reduced feeding demand requires less fluid flow to compensate for solidification shrinkage, and results in smaller pressure drops in the mushy zone. Therefore, in order to accurately describe casting defects, comprehensive models of fluid flow, heat transfer, and solidification must include the effect of microporosity as well.IntroductionIn the terminology commonly used by foundrymen, porosity is usually considered to be either ""hydrogen"" or ""shrinkage"" porosity. Hydrogen porosity is the term given to porosity that is generally rounded, isolated, and well distributed. Porosity that is interconnected or clustered, and of an irregular shape corresponding to the shape of the interdendritic region, is usually termed shrinkage. In general, the occurrence of microporosity in aluminum alloys is due to the combined effects of solidification shrinkage and gas precipitation [1]. Continuum models [1, 2- 7] have been used to predict the level of porosity in castings. A number of other studies have also attempted to understand the phenomena of porosity formation and pore growth [8-10] and pore morphology [11].The governing equations for fluid flow and hydrogen evolution indicate that porosity formation and fluid flow are strongly coupled. However, in most studies [4, 9, 10], it is considered that the porosity formation does not influence the fluid flow in the mushy zone. Kubo and Pehlke [3] presented a methodology for the prediction of microporosity distribution in shaped castings by considering the effects of both the hydrogen precipitation during solidification and the pressure drop in the mushy zone. In their approach, the local pressure and porosity were computed in an uncoupled manner based on a ""flux of interdendritic liquid"" criterion, i.e., either pressure or porosity was first computed using the other variable at the previous time step. Their approach has been used with little change in numerous studies [6, 12, 13]. Recently, Kuznetsov and Vafai [14] presented a fully coupled, one-dimensional model for the computation of pressure and porosity. They showed that neglecting the effect of porosity formation on the pressure in the mushy zone yields higher pressure drops and an over-prediction of final porosity. They also showed that the influence of porosity formation on the pressure is larger at lower pressures in the mushy zone."

Jan 1, 2001

By Rodney J. Ishak

The reduction of Mn3O4 to MnO has been investigated in a thermobalance apparatus, The charge was composed of manganese ore (decomposed by heating/calcination or pre-reduction to mainly Mn3O4) and coke. The material was charged to a crucible, which was suspended in the balance. CO-gas was distributed through a grid in the bottom of the crucible. Two sizes of ores were used; 2.4-4.8 mm and 6,7-9.5 mm. Coke particles were in the size range 4.8-6.7 mm. Experiments were conducted in the 900-1100°C temperature range. The composition of the product gas was monitored continuously. External mass transport between bulk gas and particle surface does not seem to limit the rate of reduction. Assuming that both diffusion through product layer and chemical reaction at the interface between MnO and Mn)04 are rate controlling, the data was tried both in a shrinking core model and in a grain model using regression. The grain model gives the best physical description of the process, because the reactant is in fact a porous medium. With this model the effective diffusivity was calculated to be in the 1.5-6.10.5 m2/s range. The pore size was mainly between 0.1 and 10 um,

Jan 1, 2003

By Jerome P. Downey

The Indium Corporation of America - Colorado School of Mines Indium Separation Technology was evaluated as a potential means of treating smelter flue dusts stockpiled at the Pintlar Corporation property in Kellogg, Idaho. The patented technology represents a method for segregating the contained indium, lead, and other metals in forms acceptable for downstream processing and recovery. Separation is effected by treating the dust with metallic sodium in a bath of molten lead. Process effectiveness was measured by determining the relative distribution of key metals between the bullion and dross products at small pilot plant scale. The study indicated that application of the technology to the Pitlar samples results in a highly efficient concentration of lead in the bullion, while indium is collected in the dross. The distribution of other key metals between the bullion and dross products and the effect of varying selected process parameters are also discussed.

Jan 1, 1994

By Ray Y. Lin, Randall A. Blue

"Joining of silicon carbide with infrared using a mixture of Si-30wt.%C as the brazing material has been investigated. Joining was performed at a temperature of 1500 °C in a flowing argon atmosphere for processing times ranging from 5 to 60 seconds. The joining filler materials include thin film silicon obtained by thinning down silicon wafers to about 70 /!m and graphite powder of a 15 /!m average particle size. Joint strengths were determined with a specially designed shear-in-compression jig for testing shear strengths of brittle materials. Cross section examinations of the joined specimens with optical microscopy, scanning electron microscopy and transmission electron microscopy have shown that all joints are essentially void free with excellent wetting between the base SiC and the brazing material. Silicon carbide in the B form has been identified as the reaction product in the joining zone with a transmission electron microscope (TEM) and selected area diffiaction (SAD) analysis. At 1500 °C with a joining time of 60 seconds, the joint has consisted of primarily SiC. With such a high SiC content in the joint, the joint strength is comparable to those by other joining techniques, such as diffusion bonding, as reported in the literature. A kinetic model for the formation of SiC from liquid silicon and carbon is proposed to explain the observed joint microstructural evolution.IntroductionSilicon carbide is of great interest for high temperature structural applications because of its excellent high temperature strength, wear resistance and anticorrosive characteristics [1]. Even though the interest in SiC is high, the use of the material has been limited by the high cost and difficulties involved in forming components of complicated shapes [2]. It is these limitations that necessitate the development of effective joining techniques that are cost effective and able to provide strong joints."

Jan 1, 1996

By Gordon A. Irons

"Powder injection for melt refining is widely practiced in the steel industry, and is gaining acceptance in the non-ferrous industries. In these commercially-important systems, the thermodynamics and kinetics may be very complicated. More than one element may be removed by refining, and often the refining agents are not just one compound. In this paper, the thermodynamic and kinetic aspects of these processes are reviewed. A number of examples are given, such as the desulphurization of iron with a variety of reagent mixtures, and selenium removal from copper with several different reagent combinations.IntroductionI am very pleased and honored to present a paper at this Symposium recognizing the many contributions of Professor Howard Womer. Even at the time I was an undergraduate student, the WORCRA process was part of the curriculum. I remember at the time that I was fascinated by the concept, and due to it and the many other rapid developments in Process Metallurgy, I chose it as my field of study. I think the Symposium is testimony that Professor Womer has touched the lives of many others as well.My original assignment was an overview of the basic aspects of gas and solids injection. However, I reviewed most of this material at the Savard/Lee Symposium [1]. In the present paper, I will present some of the basic issues related to refining with powder injection, using work that we have recently completed in both ferrous and non-ferrous systems."

Jan 1, 1996

By Patricio Barrios

The Rio Tinto Metal (RTMetal) copper smelter, located 5 Km from Huelva, Spain, began operations in 1970. Since then a series of expansions and modifications have allowed a progressive increase in copper production. Environmental considerations having become increasingly important, environmental protection has come to represent an important aspect of the investments in production. As a result, modifications have been carried out in the two existing acid plants: -Modification of the RTM I gas cleaning section to closed circuit. -Substitution of cascade filters and acid lines. -Modification of the RTM I plant to double absorption. The Expansion and Environmental Improvement Project, completed end 1995, will allow 270,000 t Cu and 800,000 t H2SO4 to be produced yearly, at the same time achieving a decrease in specific and overall emissions. RTMetal's goal is to be an efficient smelter, with the avowed intention of respecting the environment and adopting the best available technologies.

Jan 1, 1996

By Peter C. Hayes

"The high temperature reduction of solids through the use of reactive gas atmospheres has application in a wide range of industrially important processes. Whilst significant advances have been made in understanding and describing these processes, some key aspects of the chemical reactions and reaction mechanisms operating in these systems, for example, the transformation from metal oxide to metal, remain poorly understood. A number of different product morphologies have been identified in these reaction systems and the reaction rates have been shown to be critically dependent on the product structure.Theoretical examination of the elementary process steps taking place in the region of the gas/metal/metal oxide interface, combined with electron microscope studies of the resultant product microstructures, have enabled the key process and material variables responsible for the development of the various product morphologies to be identified. By considering i) established criteria for the stability of moving interfaces in a thermodynamic potential gradient, ii) the relative rates of chemical reactions on the oxide and metal surfaces, and iii) key process phenomena and physico-chemical properties of the solid phases, the mechanisms and conditions for the formation of various product morphologies are identified. Interestingly the analysis points to direct analogies between these phase transformations and, the phenomena and microstructures observed in metal solidification, and the potential to develop generic models of these fluid/solid reaction systems."

Jan 1, 2013

By Kumar M. Lyer

The channel reactor for ferrous and nonferrous processing has been modeled as a combination of ideal reactors. Cold model studies simulated the counter-current flow of slag and matte (or metal) with high-strength submerged gas injection. A composite model has been developed which describes the mass transfer between the two liquid phases, including the transfer of minor elements. The residence time for the matte droplets in the matte/slag emulsion is compared with the settling rates for the matte droplets in the slag to determine their relative importance in the mass transfer between matte and slag. The governing equations for mass transfer have been developed using correlations for the mass-transfer coefficients in the continuous and dispersed phases. An application of this scheme to a typical copper smelting system is presented.

Jan 1, 1993

By H. Y. Sohn, M. Pérez-Tello, P. J. Smith, K. M. Riihilahti

A three-dimensional computer model for the Kennecott-Outokumpu flash converting process for copper matte is presented. The model incorporates the transport of momentum, heat and mass, and reaction kinetics between the gas and particles in a particle-laden turbulent gas jet. The k-E model is used to describe gas-phase turbulence in an Eulerian framework. The particlephase is treated from a Lagrangian viewpoint which is coupled to the gas phase through the source terms in the Eulerian gas-phase governing equations. Matte particles were represented as Cu2S·yFeSx. Based on experimental observation, the oxidation products were assumed to be Cu2O, CuO, Fe3O4, and SO2. A reaction mechanism involving the external mass transfer of oxygen to the particle surface and diffusion of the oxygen through the oxide layers of CuzO/Fe304 and CuO/Fe3O4 is proposed. Predictions of the mathematical model were compared with the experimental data collected in a large laboratory furnace. A reasonable agreement between the model predictions and the measurements was obtained in terms of fractional conversion of the oxidation reactions and of sulfur remaining in the reacted particles. The simulation of an industrial flash converting furnace was also performed. Higher oxidation rates, more even distribution of particles, and thus a more efficient use of the reactor volume are predicted with a burner having a distributor cone, than with a single-entry burner.

Jan 1, 1999

By László I. Kiss, Verena Mackowiak, Alexandre Perron, Dominic Toulouse, Alicia Liedtke, Sándor Poncsák

"Bubbles play a very important role in different metallurgical applications like for example in electrowinning. During heterogeneous nucleation, the maximal size of the bubbles growing at the nucleation sites as well as the nucleation frequency is determined by the so-called detachment condition. Detachment occurs when the external forces acting on the bubble exceed the retaining forces along the solid-gas-liquid triple interface line. The phenomenon depends strongly on the shape and orientation of the solid surface and on the nature and strength of the external buoyancy and drag forces. In the present study the detachment conditions of bubbles from downward facing horizontal and inclined plates were studied experimentally under the effect of gravitational and hydrodynamic forces. The results show the deformation of the bubbles under the effect of the external forces and the detachment conditions as function of the bubble volume.IntroductionIn heterogeneous nucleation bubbles are generated at the so-called nucleation sites along the solid-liquid interfaces. They continue to grow there and after they reached a certain size they detach from the solid surface and leave the nucleation site. This scenario is well known both in boiling and electrolysis. During the growth period a stable equilibrium exists between the forces that retain the bubble at the nucleation site and the forces that try to remove it. This equilibrium evolves with the increasing volume of the bubble to the point when the detachment forces overcome the retaining forces.The life of a single bubble generated by heterogeneous nucleation can be divided into two periods separated by the detachment - or in other words by the departure - of the bubble: first the growth at the nucleation site and then the movement away. The knowledge of the detachment conditions makes possible the determination of the maximal volume of the bubble at the nucleation site that, in tum, makes possible the determination of the nucleation frequency. This is why so many researches have been directed toward the clarification of the details of the bubble detachment in the past decades. The equilibrium between the attaching and separating forces depend on the presence of body, surface and flow induced forces in the liquid, on the geometry and orientation of solid surface, on the properties of the solid-liquidgas system etc."

Jan 1, 2004

By Emil B. Milosavljevic, Ljiljana Solujic

Cyanide is exceptionally reactive, and in typical gold/silver processing liquors, cyanide may be transformed into various species and forms depending on the mineralogy of the ore and chemical make-up of the process water. The exact speciation and relative concentrations depend on the Eh and pH values, as well as the free CN concentration in the system. Very good cyanide balances can be achieved by the judicious selection of the analytical techniques used. The choices an analyst has to make (which analytical methods to use and which ones to avoid) in order to gain better understanding of cyanide speciation and balances in a particular system under investigation will be discussed. Examples of cyanide balances obtained for the laboratory scale tests (agitated leach and column tests) will be presented and discussed.

Jan 1, 1999