Search Documents

By Marie-Aline Van Ende, In-ho Jung

A thermodynamic database for the oxyfluoride system CaO-MgO-Al2O3-SiO2-Na2O-K2O-Li2OMnO- FeO-F has been developed based on the critical evaluation and optimization of all available experimental thermodynamic and phase diagram data. The developed database can be used for phase diagram and equilibrium solidification calculations for multicomponent systems and for understanding the solidification behavior of mold fluxes. Based on this thermodynamic database, a simple kinetic model was developed to simulate the interactions between the mold flux and molten steel using effective equilibrium reaction volumes combined with the thermodynamic database.

Jan 1, 2014

By Shufang Ding, Fukun Yan, Zhiqiang Shan, Wei Chen, Cuicui Ji

"To remove aluminum ion from chlorinated rare earth solution, this paper used hydrolysis method to explore the hydrolysis behavior of aluminum ion in aluminum chloride solution and confirm the optimum conditions of aluminum ion hydrolysis, which are pH value, temperature and initial concentration of Al203 and so on. The experimental results show that single treatment can make aluminum precipitation rates of chlorinated rare earth solution reach about 90% by hydrolysis precipitation; and then several recycle disposal can get precipitation rates of 89% for aluminum and 2.86% for rare earth.IntroductionIn China, rare earth resources are very rich and unique minerals, complete variety, and rare earth products are very large in the domestic reserves. Rare-earth and application products have been deep into all areas of our life, permanent magnet material of rare earth is one of the most popular application areas[11. Binary oxides such as praseodymium neodymium have been widely applied in the fields of glass, ceramics, magnetic materials, catalysts and so on. Especially, the advent of the Pr-Nd-Fe-B magnets which makes the world magnetic material into a new stage of development [2•3]With the development of science and technology, for industrial, physical and chemical indicators of raw materials Pr-Nd oxides (such as particle size, specific surface area and non rare earth impurities etc.) are also getting higher and higher. The oxide size has an important influence on sludge formation in the electrolytic process. If the size is too large, added oxides have settled on the bottom of slot before melting, and then generated sludge; if the particle is too small, it can cause dust dispersion, enlarge oxide unit consumption and increase the cost of production in the charging process. Some early processes use oxalic acid to make chloride neodymium praseodymium settle, and impurity can be removed cleanly, but the cost is high, it is not suitable for production. At present, most enterprises are using ammonium hydrogen carbonate to precipitate chlorinated neodymium praseodymium, but chlorinated neodymium praseodymium such as iron and aluminum and so on can easily form gel in the precipitation process, seriously affect the growth of neodymium praseodymium carbonate crystal and often leads to particle meticulous, even may also generate gel-like neodymium praseodymium sediments and cause centrifugal or suction filtration difficult. Now the actions and their removal of impurity such as iron and aluminum have done a lot of research in the production process of rare earth, removing aluminum craft with alkaline (sodium hydroxide) and acid (oxalic acid) has good effect, but the cost is higher[41; used adding complex agent to remove aluminum method which is simple and easy to operate, but aluminum removal rate is not high, and also changed the sediment of crystal type[51, and etc. This paper discusses the removal of chlorine from rare earth solution on the basis of the hydrolysis property differences betweenAJ3+ and rare earth ion."

Jan 1, 2013

Gas-liquid contacting in the packed bed is a common operation in metallurgical reactors. Research has shown that, unlike wetting flow, non-wetting liquid flows in the form of discrete droplets or rivulets. Thus, modeling of the liquid phase as a continuum is in contradiction to the observations. Also, for the non-wetting case, continuum models have failed to describe liquid flow path when the liquid source is a point source. The aim of the current work is to put forward a combined Lagrangian-Eulerian approach to model the liquid and gas flow in the packed bed. Liquid is assumed discrete and modeled using a force balance approach. Gas is assumed to be interpenetrating continua and modeled using k-emodel for turbulent flow. Structured packing is assumed and x- ray imaging technique is used to visualize liquid flow lines in the bed. Simulation results for liquid flow path compared with the experiments.

Jan 1, 2006

By Patrice Chartrand, Halvor Dalaker, Philippe Ouzilleau

A size-dependant thermodynamical model for the carbon-hydrogen previously developed by Ouzilleau et al. [1] has been expanded here to include chemisorption of methyl groups. Gibbsenergy minimalisation calculations using FACTSAGE software on this model indicates that hydrogen bonding through methyl groups is energetically favoured as an intermediate between bonding as monoatomic hydrogen to edge hexagons (which is more favourable) and as monoatomic hydrogen to corner hexagons (which is less favourable). The model has also been applied to methane decomposition and oxide reduction using natural gas. A C-H solid solution as a thermodynamic description of the solid carbon phase influences calculations of carbon activity in metastable methane, and gives different results than when using graphite.

Jan 1, 2015

By Avijit Moitra

The behavior of the solidifying shell in the early stages of solidification has an important influence on the final quality of continuously-cast steel slabs. In order to understand the thermal and mechanical behavior of the shell, a two-dimensional transient piecewise-coupled finite-element model has been developed. The model simulates a transverse section of the slab as it moves down through the mold and incorporates the effects of heat conduction, solidification, shrinkage, turbulent fluid flow, thermal distortion of the mold and the visco-plastic behavior of the steel. Coupling between the thermal and the mechanical model is based on the mutual dependence of heat transfer across the interface between the shell and the mold and the size of the gap. The effects of mold distortion and taper on the gap size are also included. The effect of fluid flow has been incorporated via a heat flux imposed at the solid-liquid interface, which is obtained from a separate fluid flow model. The high temperature creep and plasticity of the steel is incorporated through a unified constitutive law defining the inelastic strain rates as a function of temperature, time and stress state. The model can be applied to various problems in continuous casting, such as the formation of surface defects and the design of mold taper.

Jan 1, 1992

By Michael Zinigrad

The quality of metallic materials depends on their composition and structure and these are determined by various physico-chemical and technological factors. To effectively prepare materials with required composition, structure and properties it is necessary to carry out a research in two parallel directions: Comprehensive analysis of thennodynamics, kineties and mechanisms of the processes taking place at the solid-liquid-gaseous phase interface during welding processes and development of mathematical models of the specific welding technologies. We have developed unique method of mathematical modeling of phase interaction at high temperatures. This method allows us to build models taking into account the thennodynamic characteristics of the processes, the influence of the initial composition and temperature on the equilibrium state of the reactions, the kinetics of heterogeneous processes, the influence of the temperature, composition, hydrodynamic and thennal factors on the velocity of the chemical and diffusion processes. The model can be implemented in the optimization of various technological processes in welding, surfacing, casting as well as in manufacturing of steels and non-ferrous alloys, materials refining, alloying with special additives, removing of non-metallic inclusions.

Jan 1, 2003

By B. Q. Li

A numerical study of the developing fluid flow and thermal aspects during the staning phase of aluminum continuous casting processes is presented. The deforming finite element method, coupled with a quasi-Lagrangian formulation, is used to represent the growth of an ingot and the dynamic fluid flow and thermal behavior that evolves in the growing ingot. The mathematical formulation of the problem and the numerical treatment are discussed. The algorithm solves the free moving nodes as part of total unknowns with an automatic time step control for time integration. This permits an optimal computing efficiency while still keeping the computational errors under control. A selection of the results obtained using the algorithm is presented. The results are concerned with the evolution of fluid flow, temperature and solidification phenomena during a DC round ingot casting process, as it evolves from the beginning of casting operation to a steady state. These results show that the time-varying, complex fluid flow and thermal phenomena during continuous casting processes can be very well represented by the computational algorithm. The results also illustrate that, during the casting process, ~e fluid flow and temperature fields change drastically at the initial stage but evolve slowly afterwards

Jan 1, 1993

By B. C. Blakey

Unlike most hydrometallurgical slurries, those containing significant concentrations of goethite are typically highly viscous and shear-thinning, even at solid volume fractions below 5%. The viscosity may also depend upon time. These characteristics must be taken into consideration in slurry transport and heating. The technical literature is replete with apparent contradictions regarding the viscous behavior of these slurries, which may be due, in part, to variations in viscosity-measuring techniques. We present techniques that yield consistent results suitable for use in process design. A striking degree of time-dependent behavior is demonstrated for a laterite slurry. Reliable methods to design and analyze tubular transport and heating systems for time-independent slurries are summarized. Rules of thumb are then offered to account for the effects of time-dependency.

Jan 1, 2000

By Michael Zinigrad

The quality of metallic materials depends on their composition and structure and these are determined by various physico-chemical and technological factors. To effectively prepare materials with required composition, structure and properties it is necessary to carry out a research in two parallel directions: Comprehensive analysis of thermodynamics, kinetics and mechanisms of the processes taking place at the solid-liquid-gaseous phase interface during welding processes and development of mathematical models of the specific welding technologies. We have developed unique method of mathematical modeling of phase interaction at high temperatures. This method allows us to build models taking into account the thermodynamic characteristics of the processes, the influence of the initial composition and temperature on the equilibrium state of the reactions, the kinetics of heterogeneous processes, the influence of the temperature, composition, hydrodynamic and thermal factors on the velocity of the chemical and diffusion processes. The model can be implemented in the optimization of various technological processes in welding, surfacing, casting as well as in manufacturing of steels and non-ferrous alloys, materials refining, alloying with special additives, removing of non-metallic inclusions.

Jan 1, 2003

By R. J. Kuczynski

The U.S. Bureau of Mines Reno Research Center operated a batch pilot plant to demonstrate high-temperature cyanide leaching for recovering platinum group metals (PGM) from automobile catalysts. Approximately 1,600 kg of used pellet, monolith, and metal support catalyst containing 1,680 g (54 tr oz) of PGM were processed. Forty-five-kilogram batches of used catalyst were leached with sodium cyanide solution at 160° C for 1 h under basic conditions in a countercurrent processing sequence to dissolve the PGM. Extractions from the used pellet catalyst ranged from 94 to 95 pct for Pd, 95 to 97 pct for Pt, and 64 to 81 pct for Rh. Extractions from the used monolith catalyst ranged from 7B to BB pct for Pd, 75 to 90 pct for Pt, and 43 to 71 pct for Rh. Heating the pregnant leach solutions to 275' C for 4 h destroyed the PGM-cyanide complexes, resulting in over 99.7 pct of the PGM precipitating from solution. The PGM precipitate was predominantly a powder metallic concentrate, typically analyzing greater than 50 pct PGM. Heating destroyed cyanide to less than 0.2 mg/L. Both the pellet and monolith residues were evaluated for disposal using the EPA Toxicity Characteristic Leaching Procedure.

Jan 1, 1995

By L. R. Verney

About 75% of the market economy countries's supply of cobalt is produced in Central Africa by Zafre and Zambia. Zafre alone accounts for more than 55% and has the resources and capacity to increase output significantly at any time so its dominant position is unlikely to be challenged in the foreseeable future. Other producers from domestic resources are Canada, Australia and South Africa; and Cuba, probably the most important producer outside of the Market Economy countries. Belgium, Norway, France, Japan and Finland produce cobalt from imported materials. While there are "cobalt ores", inMorocco, USA, Canada and the USSR, the mineralisation is complex and cobalt extraction is costly. In ZaPre and Zambia cobalt is a by-product of copper; in Canada, Australia, France, and Cuba it is a by-product of nickel; and in South Africa it is a by-product from the production of Platinum Group Metals. Thus the levels of cobalt production are inevitably related to the production of other primary metals. While some cobalt is produced by predominantly pyrometallurgical methods most of the world's cobalt is produced hydrometallurgically. The existence of large hydro-electric power plants and the mineralogy of the copper and cobalt concentrates encouraged research and development in Zafre of the recovery of copper and cobalt by electrowinning from sulfate solutions; much pioneering work was carried out, which lead to construction of the two largest copperlcobalt hydrometallurgical plants in the world, at Shituru and Luilu. Similar systems were adopted in Zambia. In Canada high pressure hydrometallurgical processes based on the sulfate system were developed and adopted in Australia, the Philippines, Finland and South Africa. Meanwhile developments in chloride hydrometallurgical extraction of nickel and cobalt lead to its use in the extraction of cobalt in Norway, France and Japan.

Jan 1, 1988

By Z. Zhang, Cuihuan Huang, Zongshu Zou, Nan Wang, Xueqian Xin

"Vitrification is considered as an attractive procedure for municipal solid waste incineration ash, which can realize the volume reduction and innocent treatment of incineration ash, as well as reuse of bottom ash. The main oxide components of molten ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the total mass. The phase relations and thermodynamic properties of the CaO-Al2O3-SiO2-FeOx-MgO-Na2O oxide system is highly required, and is of great scientific significance for optimization of vitrification processing and sustainable resource utilization of melting slag. A study on the equilibria phase relations of CaO-SiO2-MgO-FeOx system was done by using CALPHAD method based on FactSage in this paper. The modeling parameters for the thermodynamic properties of liquid phase in CaO-SiO2-MgO-FeOx system were established and the equilibrium phase relations of MgO-SiO2-FeOx and CaO-SiO2-FeOx-MgO systems were calculated for different temperatures and oxygen partial pressures.IntroductionThe main oxide components of vitrified bottom ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the bottom ash by weight [1]. During slag processing and modification, the knowledge of thermodynamic properties and liquidus temperature in the related slag system is highly required [2-5], which is not yet available. Through literature survey [6-9], it is clear that the systematic information on the concerned complex slag system is scarce. Most binary subsystems except FeOx-Na2O have been investigated well. Among ternary subsystems, few phase relations of the Na2O-MgO-SiO2 ternary system are available. For the phase relations of the system Na2O-MgO-Al2O3, all the studies are focused on the Al2O3-rich region. Investigation on the CaO-Al2O3-FeOx system is limited to Fe2O3-containing system with relatively higher oxygen potential. Most quaternary systems are not studied well except the CaO-MgO-Al2O3-SiO2 system, mainly due to their metallurgical importance. Figure 1 demonstrates the research status of the vitrified bottom ash slag with almost zero effort [10]. The effort here is defined based on the published literature by considering the number of publications, the investigated composition ranges, and the research details. So far the engineers in the field have to make assumptions of the thermodynamic properties of the simplified oxide system, without taking into consideration the interactions of the different oxide components, which hinders the development of the slag valorization and utilization. In order to provide thermodynamic properties for the application of the vitrified bottom ash, the six-component oxide system (CaO-MgO-Al2O3-SiO2-FeOx-Na2O) will be investigated through both experimental approach and computer modeling."

Jan 1, 2011

By D. Van Dooren

The final goal of the research project is to develop a 3D FEM model that is able to predict the kinetics and micro-structural evolution during the bainitic transformation. The input parameters consist of thermodynamic and atomic mobility data obtained from the ThermoCalc and mCTRA databases combined with structural mechanics data extracted from the stress-strain curves of the fcc and bee phases. In this paper the general principles of the model are outlined and some interesting preliminary results are shown and commented. The full implementation of the model has presently not been achieved yet. In the model the bainitic transformation is considered as a sequence of martensitic (re)nucleation and growth of a ferritic subunit followed by the carbon rejection into the surrounding austenite. The (re)nucleation of the subunits will be described through a non-classical martensitic nucleation criterion. Once a nucleus has been activated at a specific location in the material, a full-sized subunit is instantaneously formed through a displacive mechanism. The stress state in the system that arises due to the transformation strain can be calculated by a 3D FEM programming code. Immediately after the formation of the subunit, another 3D FEM programming code calculates the carbon diffusion from the supersaturated ferrite into the surrounding austenite. The resulting stress state and carbon profiles will be used to determine where and when a new subunit will nucleate based on a renucleation criterion. Keywords: Bainitic Transformation, Modeling, Eshelby, Carbon Diffusion

Jan 1, 2003

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 Leiv Kolbeinsen, Stian Seim, In-ho Jung

"The current work presents new experimental data in the iron-unsaturated region of the FeTiO3-Ti2O3-TiO2 slag system. The samples are prepared by melting pure reactants in a high frequency induction furnace that employs a cold crucible. A similar experimental set-up has been described in literature and proven suitable to investigate high titania slags. The FeO content of the samples range from 3.7 to 21.8 wt% and the Ti2O3 content range from 3.6 to 30.1 wt%. The liquidus temperatures of the samples are measured in-situ by a spectropyrometer and range from 1450 to 1645 °C.In addition, an improved thermodynamic database for the FeO-Ti2O3-TiO2 system has been developed. Ternary parameters have been included and optimized to fit previously published experimental data. This optimization minimizes the discrepancy between experimental data and thermodynamic calculations as previously discussed in literature. New liquidus projection plots are proposed for the FeO-Ti2O3-TiO2 and the FeTiO3-Ti2O3-TiO2 systems.IntroductionIlmenite (FeTiOs) smelting is a relatively small industry world-wide. However, a reasonable focus on the process has been applied in Norway due to the location of one such smelter in Tyssedal, which is located in the western part of Norway. The process is essentially carbothermal reduction, where most of the iron in the ilmenite is reduced to its metallic state, and the titanium oxide is concentrated in the slag product. The metallic iron is sold as a high purity pig iron and finds applications in cast products. The slag concentrate is further processed for the production of TiOvpigment and/or titanium metal. This further processing can be performed through different routes according to the purity of the slag concentrate."

Jan 1, 2012

By J. E. Dutrizac

A mineralogical study of a weak acid leach residue from the Clarksville zinc plant of Savage Zinc Inc. was carried out. The study focused on Pb and Cd as these elements most significantly impact on the environmentally acceptable disposal of the residue. The residue consists of major amounts of bassanite, zinc ferrite and various Zn-Pb-Fe-Cd silicate species. Also present are lesser quantities of PbSO4, sphalerite, Fe2O3 quartz, Mn-Pb-Fe oxides, SrS04, (Pb,Sr)SO4 iron gel-silica gel, jarosite and Ti oxide. The principal Cd carriers are the zinc ferrite, which contains up to 9.00% Cd and likely accounts for -45% of the total Cd content of the residue, and the various silicate species which contain up to 6.97% Cd and account for about 45 % of the total Cd. The sphalerite is a minor Cd carrier containing an average of 0.35 % Cd and accounting for -5 % of the total Cd; the other carriers contribute only trace amounts to the total Cd content. The major Pb carriers are PbS04, Pb-bearing silicates and Mn-Pb-Fe oxides. Minor proportions of the total 1.09% Pb content of the residue are carried by SrS04 and (pb,Sr)S04' Trace Ph carriers include the iron gel-silica gel, Fe-Zn-AI oxide and bassanite. The residue after the toxicity characteristic leaching procedure (TCLP) is mineralogically very similar to the initial weak acid leach residue; the amounts of calcium sulphate are approximately the same in the two products. The principal Cd and Pb carriers are also the same as those noted in the initial residue, except that some dissolution and reprecipitation of Pb-Sr sulphate takes place. That the residue fails the TCLP test is likely a consequence of the superficial dissolution of Pb and Cd from species such as PbS04 or Zn-Pb-Fe-Cd silicate.

Jan 1, 1995

By J. Priede, G. Gerbeth

"Two different instability mechanisms of electromagnetically levitated bodies are analyzed. The first is due to the virtual coupling between the electric current passing through the magnetic system and the variation of position of the body. This mechanism can result in unstable mass center oscillations of a levitated solid body. Another type of instabilities may occur because of the coupling between the motion and the electric currents induced in the body. This effect can cause a spontaneous rotation of the body setting in as the frequency of the alternating magnetic field exceeds certain critical threshold depending on the configuration of the field. This instability can be suppressed by an axial steady magnetic field of strength comparable to that of the levitating field. 1 IntroductionAn alternating magnetic field interacting with eddy currents induced in a conducting body causes repulsion between the body and the coil generating the field. Besides, the eddy currents provide a contactless heating of the body. In such a way metallic samples can be levitated and melted without a contacting crucible. This technique allows to avoid contamination of the melt with container material and so to achieve a considerable super-cooling of the melt before it solidifies. Nowadays electromagnetic levitation is widely used in material research for measuring of the thermophysical properties of molten metals (2) .It has been observed since early fifties when the first experiments on the electromagnetic levitation were done that under certain circumstances solid levitated samples start to rotate or oscillate [l]. Surface oscillations can appear in addition when the sample is melted. Such phenomena are undesirable because they often result in failure of the levitation. Recently we showed that rotational as well as oscillatory instabilities can have electrodynamic origin related to additional eddy currents induced by motion of the body in an alternating magnetic field [3] , [4].In the first part of the present paper we analyze another possible cause of oscillatory instability due to the coupling between the electric current passing trough the magnetic system with variation of the position of the levitated body. The second part of the paper deals with the origin and suppression of rotational instability in a uniform alternating magnetic field."

Jan 1, 1999

An iridium oxide coated titanium electrode was tested as anode in copper electrowinning. Initial results confmed that the DSA-type anode was significantly more active for oxygen evolution than traditional lead anodes. However, during longer runs, the anode potential was observed to increase linearly at a rate of 220 mV/year. Scanning elecuon microscopy (SEM) and energy dispersive spectroscopy (EDS) showed that the anode passivation could be attributed to elecuochemical dissolution of the coating. The effect on the anode potential of organic additives (glue and thiourea) and lead in solution was also examined. A preliminary economic evaluation of the anodes is given.

Jan 1, 1992

By N. L. Piret

In copper smelting minimization of solid waste generation is receiving increased attention with more stringent environmental legislation and lower disposal space availability. Copper smelting slags generally being valorizable, solid waste generation is attributed to the presence in the feed of unvalorizable impurities which do not report to the slag and to the unavoidable formation of contaminated dilute acid solutions which need neutralization. As to unvalorizable impurities, solid waste minimization is achieved by rejecting them in the highest possible concentration. Dilute acid is mainly due to the formation of SO3 in the smelter gases and to the discard of decopperized bleed-off electrolyte. Its generation is substantially lowered by preventing SO3 formation, by converting the dilute acid to a valorizable product, e.g., by thermal decomposition for H2S04 recovery or by precipitation as chemical gypsum, and by suitable treatment of the bleed-off electrolyte for impurity removal. Industrial processes are evaluated and alternatives are discussed.

Jan 1, 1994

By C. Lupi

Zinc impure solutions as spent electrolytes, leach liquors coming from aqueous treatment of both minerals and solid waste, need to be purified before undergoing the treatment to obtain the final product. Solvent extraction is one of the most selective operations particularly when many metallic ions are present in solution. Zinc pure solutions are frequently obtained using DZEHPA as extractant. In this work an investigation on zinc extraction effectiveness of naftenic acid was carried out. After determining the best diluent and the optimal extractant concentration, the partition coefficient was determined as a function of temperature, equilibrium pH and zinc concentration. Finally same batch tests to determine the equilibrium curves at room temperature on exhausted electrolyte coming from zinc cell were carried out by using naftenic acid, D2EHPA and TBP. The pH giving, for each extractant, the best extraction yield was selected in order to compare the equilibrium curves. Experimental results show that all the examined extractants are very effective in zinc extraction if the process conditions are appropriately selected. In order to avoid an impure solution pre- treatment and to obtain the maximum ertraction yield the appropriate solvent can be chosen.

Jan 1, 1998