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By C. A. Morais

The present work describes the development of an efficient and relatively simple process to obtain high grade CeO2 from a mixed rare earth chloride solution. The process involves cerium oxidation and precipitation by addition of a KMnO4-NaCO3 solution. The experiments were carried out at room temperature (25 1° C). The results indicated that the major parameters affecting cerium recovery are the molar ratio of KMnO4/Ce, the initial acidity of the chloride feed solution and final pH of Ce(OH)4 precipitation. In strong acid solutions (pH < 1), the oxidation of Cl to Clo took place in addition to the oxidation of Ce(III) to Ce(IV), so increasing the permanganate consumption. Conversely, low acidity (pH >3) led to coprecipitation of the other rare earth elements. Under the selected conditions, cerium was selectively precipitated as ceric hydroxide, together with some manganese dioxide. Further purification was carried out by the dissolution of Ce(OH)4 in HCl, followed by precipitation as cerium carbonate. The filtrate was neutralised with a Na2CO3 solution in order to recover the associated rare earth elements for further separation. The final product, assaying 99.7 % CeO2, was obtained with a recovery of nearly 100%.

Jan 1, 2003

By Maria Cristina Ruiz

The removal of iron from the leaching circuits is a common problem in the hydrometallurgical processing of non ferrous metals. Among the currently available processes, hematite precipitation is the most recommendable from an environmental point of view. This paper is concerned with the batch precipitation of hematite from ferrous sulfate solutions. One of the main objectives of the study was to determine the effect of the experimental conditions on the extent of iron precipitation as well as the purity and the particle size distribution of the precipitates. The main variables studied were temperature (180 to 220 ºC), concentration of sulfuric acid (1 to 10 gpl), initial iron concentration (1 to 15 gpl) and partial pressure of oxygen (3 to 7 atm). The results showed that increasing the oxygen partial pressure from 3 to 7 atm produced a very small increase on the rate of hematite precipitation indicating that a large partial pressure of oxygen is not needed for an effective ferrous to ferric oxidation. An increase in the temperature produced finer precipitates with lower sulfur contents. On the other hand, an increase in sulfuric acid concentration and initial iron concentration produced precipitates with larger particle sizes and higher sulfur contents.

Jan 1, 2006

By Yoshio Waseda

A laser flash method has been applied to obtain the thermal diffusivity values of Zr55Al10Ni5Cu30 alloy in the liquid, glassy, crystallized and supercooled liquid states. The electrical resistivity of this particular alloy was measured in the glassy, and crystallized states by a direct current four probe technique. A specific heat of Zr55Al10Ni5Cu30 alloy was also determined by a differential scanning calorimeter in the glassy state. On the other hand, thermal diffusivity values for two alloys of Zr60Al15Ni25 and Zr65Al7.5Cu27.5 were measured in the crystallized and liquid states. The thermal diffusivity values of three Zr-based alloys in the liquid state are summarized in the linear equations with positive temperature dependency and it is noted that the lower the thermal diffusivity values of Zr-based alloys at liquidus temperature, the lower the critical cooling rate to obtain metallic glass phase becomes. The thermal diffusivity values of Zr-based alloys were compared with those of Pd-based alloy case. These results suggest that thermal diffusivity of alloy liquids might be an indicator of the glass-forming ability of Zr-based and Pd-based alloys.

Jan 1, 2006

By M. I. Zinigrad

A model of an ideal associated solution is presented. This model takes into account the existence of complexes of various compositions, sizes and geometries and allows calculating thermodynamic properties and phase diagrams of binary alloys. The model has been used formerly to calculate thermodynamic parameters and the position of the liquidus line for binary eutectic systems and also those having a stable compound in the solid phase. In all the cases the model parameters were not adjusted rather estimated from melting temperatures of the components. The recent studies dealt with the influence of arbitrary-stoichiometry associates on the equilibrium thermodynamic properties of liquid alloys. The application of the model to eutectic systems and systems having an unlimited solubility in solid and liquid states close to liquidus has been considered. It was shown that if the difference in melting temperatures of the components was small, different types of fusibility diagrams were possible: eutectic diagrams, cigar-shaped diagrams or diagrams with upper or lower azeotropic points. Peritectic transformations could take place when the difference in melting temperatures of the components was large. The present work is devoted to calculation of phase diagrams and thermodynamic properties of binary systems on the basis of chrome.

Jan 1, 2006

By E. J. Peuraniemi

Recently commissioned Kennecott-Outokumpu flash converting was developed to replace the approved but environmentally outdated Peirce-Smith -converting to satisfy the globally tightening emission regulations. In the present study, dust formation and reaction mechanisms of two copper mattes with different experimental parameters were studied in lean suspension conditions. Both mattes had very high copper content of approximately 75 wt% and low iron content of 4.5 wt% and 1.2 wt% Fe. A laboratory scale, vertical laminar-flow furnace with a low feeding rate was used to simulate the phenomena taking place in the reaction shaft of a flash converter. Experimental conditions included temperature of 1300 °C with reaction gas oxygen contents of 20 vol%, 50 vol%, and 75 vol%. In the experiments, sieved particle fractions were fed to the furnace and sampled after short reaction time intervals by quenching them into a water film. Collected particles were analysed chemically for their main elements to define their removal rates. Also, optical and scanning electron microscopy with EDS-analyser were applied to determine phenomena occurring during reactions. Kinetics of oxidation as well as ignition of particles are discussed. Changes in particle morphology, size, and composition are reviewed to describe dust formation and reaction mechanisms.

Jan 1, 1999

By T. Takasu

Overall productivity in copper refining is currently determined by the electrorefining process. Previous research showed that forced convection of the electrolyte improves the morphology of the copper deposit on the cathode and suppresses passivation of the anode. In this paper, electrorefining experiments under forced convection were carried out in the presence of As, Sb and Bi impurities, both in electrolyte and in the anode, to determine the effect of the impurities on the electrorefining process. The concentrations of the impurities in the deposit increased with increasing current density without forced convection. An increase in the fluid velocity suppressed the increase in impurity concentration. These concentrations were high, especially in the initial stage of deposition without forced convection, corresponding to a decrease in the cathode potential measured during that period. This indicates that the enrichment of impurities was induced electrochemically. The reason for the decrease in cathode potential was the low concentration of copper ions on the electrode surface because of ion consumption by the electrolysis. The forced convection of the electrolyte enhanced the ionic mass transfer and thus suppressed the polarization and deposition of the impurities. The fluid motion was shown to be effective in achieving electrolysis under high current density conditions.

Jan 1, 1999

Lance based copper-nickel matte converters have become an established technology in the field of base metal sulphide smelting and converting. An Ausmmelt® converter is currently being constructed at Anglo Platinum in South Africa to convert a nickel-copper rich matte containing platinum group metals (PGM&apos;s). The accurate prediction of the matte chemistry is required to control the composition at the endpoint which influences segregation of PGM&apos;s during the subsequent slow cooling and magnetic separation processes. A hybrid modelling approach is introduced in this paper that incorporates both the effect of thermochemistry and system dynamics. It will be shown how the model relates to fundamental conservation laws, while still providing enough flexibility to adapt to changing operating conditions. It will also show how off-line modelling can be incorporated into a robust on-line model. Based on the data from many pilot plant trials, the model prediction performance is shown to be within the accuracy requirement set by industry and therefore constitutes a reliable basis for model based control. The final generic model structure takes on the form of an thermodynamically integrated ARMAX hybrid model. The final model has the advantages of being dynamic, adaptive, robust and it can be related to thermochemical fundamentals.

Jan 1, 2002

By Victor Bredykhin

The report is devoted to the investigation and improvement of processes taking place at contact of large quantities of water insoluble liquid and particles of solid phase in a pulp. Theoretical analysis and simulation of acting conditions have allowed to determine that after attaching of oleophilic particles on the «water-reagent» separation surface the break of a formed complex is taking place according to the reagent volume and for oleophobic minerals along the «solid-reagent» separation surface. As a result particles are selectively treated if the magnitude of the reagent adhesion to the surface of solid phase in water is great. The results of dispersion are influenced significantly by availability of sharp edges on the surface of real particles. They keep tree phase perimeter of moistening. It is possible to fix reagent in the form of lens whose contact angle is significantly smaller in comparison to the thermodynamic angle. In adhesion dispersion the reduction of reagent volume, covering the equal area of particles surface is possible when the reagent is in a pulp in the form of thin films on the «water-gas» separation border. The process is tested in laboratory conditions as well as at pilot concentrating mills in flotation of sulfide ores, non-ferrous metals (copper-molybdenum ore), native sulfur and coal.

Jan 1, 2006

By Pekka Taskinen, Hannu Johto

"Copper sulfide concentrates often contain impurities such as lead and iron. The phase stabilities of the sulfide impurity systems in metallurgical process conditions are in many cases unsatisfactorily known. Thermodynamic information of a system gives better understanding of its behavior of metal making processes, but also has effects on the economic and environmental factors of the production process. In this study, isothermal equilibrium and quenching experiments of the stable phases of the system Cu2S-FeS-PbS at 700 and 900 °C were carried out and based on the experimental results, Gibbs triangle of equilibrium phases of the system was outlined.IntroductionThe knowledge of stabilities of phases and the thermodynamic properties of many sulfide systems in the temperature range of 500-1200 °C are quite limited. Especially, the knowledge of liquidus surfaces of multicomponent sulfide systems is essential for making many metallurgical processes more environmental friendly and allowing the utilization of complex concentrates. In this work, the aim was to investigate the phase stabilities of the quasiternary system CU2SFeS- PbS using evacuated silica ampoules. Of greatest interest were the properties of the liquidus surface in the system, in order to be able to predict better the formation of a liquid phase in metallurgical processes."

Jan 1, 2012

By Rafael Padilla

The recovery of copper from chalcopyrite concentrates by leaching is difficult due to the slow dissolution kinetics of this mineral in most leaching media. However, recovery of copper from sulfidized chalcopyrite (a mixture of CuS and FeS2) by leaching is faster and could be selective depending on the leaching media. In this paper, the result of an investigation on the H2SO4-O2 pressure leaching of sulfidized chalcopyrite is presented. The variables considered in the study were stirring speed, concentration of sulfuric acid, temperature, and partial pressure of oxygen. The experimental data indicated that stirring speed over 500 rpm and sulfuric acid concentration over 0.1 M had very little effect on the leaching rate. An increase in temperature from 90 to 100 ºC increased both copper and iron dissolution; however, further increase to 120 ºC affected negatively the copper dissolution. Oxygen partial pressure was found to be the main variable that controls the copper/iron selectivity of the leaching. An increase in oxygen partial pressure increased significantly the rate of copper dissolution but deteriorated the copper/iron selectivity. The analysis for sulfur of the leaching solid residues indicated that most of the copper sulfide sulfur in the sulfidized concentrate oxidized to elemental sulfur.

Jan 1, 2006

By Teruo Tanabe

The hydrogen-absorbing materials are expected to have the following properties at moderate conditions, (a) a large capacity of hydrogen absorption, (b) the absorption rate of hydrogen is large and (c) hydrogen-absorbed materials can easily desorb hydrogen. Thus the three concepts of capacity, rate and reversibility seem to be indispensable to clarify the mechanism of hydrogen absorption by the materials. In this work, the amount of absorbed hydrogen, the absorption rate and the reversibility of hydrogen absorption- desorption reaction were measured for binary R-M systems (R = Y, La, Ce; M = Co, Ni). These experimental results were discussed by the following three physical properties that were calculated by the extended Hückel method, i.e. the density of states unoccupied by electrons, the cohesive energy and the energy fluctuation. The major results are as follows: (a) the amount of absorbed hydrogen increases with the density of states in the energy range between -9 and -4 eV, (b) the R-M compounds of which energy fluctuations are large show a large value of rate of hydrogen absorption, and (c) when the cohesive energy is large, the compound has a tendency not to easily desorb hydrogen, i.e. its reversibility is poor.

Jan 1, 2006

By Damien Wagner

To reduce the emission of greenhouse gases by the steel industry, particularly for ironmaking, the production of DRI (Direct Reduced Iron) using hydrogen as the reducing gas instead of carbon monoxide is being considered. In this context, the reduction of pure hematite by hydrogen was studied at the laboratory scale, varying the experimental conditions and observing the rate and the course of the reaction. All the reduction experiments were performed in a thermobalance and supplementary characterization methods were used like scanning and transmission electron microscopy, X-ray diffraction, and Mössbauer spectrometry. The influence of rising temperature in the range 550-900°C is to accelerate the reaction; no slowing down was observed, contrary to some literature conclusions. A series of experiments consisted in interrupting the runs before complete conversion, thus enabling the characterization of partially reduced samples. Interpretation confirms the occurrence of three successive and rather separate reduction steps, through magnetite and wustite to iron, and illustrates a clear structural evolution of the samples. Finally, the influence of the sample type was revealed comparing a regular powder, a nanopowder and a sintered sample. The regular powder proved to be the most reactive despite its larger grain size, due to a more porous final structure.

Jan 1, 2006

By A. J. Duncan, S. Viswanathan, Q. Han

"Measurements of liquid permeability in the mushy zones of Al-15.42% Cu and Al-8.68% Cu alloy samples have been performed isothermally just above the eutectic temperature, using eutectic liquid as the fluid. A modified method has been developed to determine the specific permeability, Ks, as a function of time during the test from the data collected on these alloys. Factors affecting permeability measurements are discussed. Permeabilties are observed to vary throughout the experiment. This is attributed to rnicrostructural coarsening and channeling that occurs in the sample during the experiment. The permeability is related to the rnicrostructure of the sample using the Kozeny-Carman equation. The correlation between the measured Ks, liquid fraction, gL and the specific solid surface area, Sv, improves markedly when compared to previous studies in which rnicrostructural coarsening was ignored.IntroductionThe permeability of interdendritic liquids flowing through dendritic structures ·is an important parameter needed to predict the level of porosity in castings. The permeability is a component of Darcy's Law, used to estimate the pressure drop due to the resistance to the flow of interdendritic fluid to feed shrinkage. Therefore, much research has focused on measuring the permeability of alloys in the mushy zone (1-10). The Kozeny-Carman equation for liquid permeability in the mushy zones of alloys may be written as"

Jan 1, 1999

By G. Gerbeth, Y. Gelfgat, A. Cramer, A. Bojarevics

The production of highly porous metallic substrates requires an effective and well controlled production of metallic fibres with diameters in the range of 50 to 200 microns. The melt extraction, where a quickly rotating wheel extracts fibres directly out of the inductively heated melt, is a promising technology for that purpose. The main limitations of this process are due to turbulence within the melt and a wavy motion on the surface. Both effects give rise to strong and time dependent deformation of the melt surface which, in turn, causes non-stationary conditions of the contact zone between the extraction wheel and the melt. In the patent literature many examples can be found which try to overcome these problems by submersing mechanical parts directly into, or placing them at least in close vicinity to the melt, aiming at a stabilisation of that contact region. Even made of heat resistant ceramics they suffer from corrosion or cracks and do not work reliable at all. The present work describes a non invasive control mechanism by means of a magnetic field. Model experiments were carried out to study the calm down of the turbulent surface of a inductively stirred melt. The stabilisation of the melt surface has been demonstrated in practise by the installation of a solenoid at a working extraction facility under rough industrial conditions like a powerful induction heating and vacuum.

Jan 1, 1999

By Jie Li, Shu Yang, Zhongliang Tian, Xun Hu, Yanqing Lai, Shaolong Ye

The electrolyte with high solubility for Sc2O3 is very important to realize the preparation of Al-Sc master alloy by the molten salt electrolysis. The solubility of Sc2O3 in K3AlF6- Na3AlF6-AlF3 melts is determined with an isothermal saturation method. The effects of KR (ratio of K3AlF6 to K3AlF6+Na3AlF6), the concentration of Al2O3 and the temperature on the solubility of Sc2O3 are also investigated. The results indicate that the solubility of Sc2O3 in K3AlF6-Na3AlF6-AlF3 melts increases and then decreases with KR increasing. The solubility of Sc2O3 is 8.698 wt.% in (K3AlF6-Na3AlF6)(KR25%)-18 wt.%AlF3 melts at 940℃. The effect of temperature on the solubility is little, and the values are 8.575 wt.% and 8.762 wt.% respectively when the temperatures are 930℃ and 960℃. The solubility decreases from 8.809 wt.% to 7.058 wt.% as the concentration of Al2O3 increases from 1.5 wt.% to 5.0 wt.% at 950℃.

Jan 1, 2015

By R. D. MacDonald

The papers presented in this chapter cover a wide range of hydrometallurgical topics and might be considered to be unrelated to each other. All of the authors, however, utilized the basic methods of process mineralogy to characterize the reactants in their experiments and the products produced. The wide range of research topics which can be pursued successfully by the use of the methods of process mineralogy is a matter of interest in itself. One might speculate that the methods could be even more widely applied if only their utility were better recognized. These methods for characterizing reactants and products include principally x-ray diffraction, optical micros-copy, wet chemical analyses, instrumental chemical analyses, high intensity magnetic separation, micro-scale gravity separation, differential thermal analysis, micro-hardness testing, and judicious use of the sledgehammer and cold chisel. It is perhaps not by coincidence that most of the papers in this chapter were prepared not by mineralogists, but by hydrometallurgists, who are recognizing the importance of thinking in terms of mineral phases, and not just assays! It appears that the gap between process mineralogy and the mineral industry is closing, and that future AIME sessions promise to become established forums where mutual discussion of such topics as metallurgical "troubleshooting" and process design may become commonplace between plant engineer and process mineralogist.

Jan 1, 1981

By J. E. Dutrizac

The behaviour of the lanthanide elements during the precipitation of sodium and potassium jarosites at 98oC from sulphate media was systematically investigated. The lower atomic weight lanthanide elements (La to Gd) are characterized by the limited solubility of their alkali-lanthanide sulphates, such as NaNd(SO4)2?H2O, which commonly contaminate the jarosite precipitates. Hence, single phase jarosite-type compounds were precipitated only from solutions containing <0.4 g/L of the La to Sm lanthanides. The sulphates of the heavier atomic weight lanthanide elements (Tb to Lu) have significantly higher solubilities such that solutions containing up to 10 g/L of the individual lanthanides could be investigated without the precipitation of alkali-lanthanide sulphate species. Even at the highest lanthanide concentrations, however, none of the jarosite precipitates incorporated more than 0.3 wt% of any of the lanthanide elements. Comparable levels of lanthanide incorporation were noted in both Na-jarosite and K-jarosite. Although the mass of the jarosite precipitate increased with increasing ferric sulphate concentration or with increasing pH, the extent of lanthanide incorporation was not significantly affected. Clearly, the trivalent lanthanide elements do not substitute extensively for trivalent iron in the jarosite structure. This behaviour likely reflects the significantly lower hydrolyzability and larger size of the trivalent lanthanide ions relative to ferric ions.

Jan 1, 2003

By Peng Fan

Nitride capacity is usually employed as the measure of slag?s ability to remove nitrogen from liquid metal, since nitrogen distribution ratio between slag and metal can be calculated from nitride capacity provided that the value of oxygen activity in liquid metal is available. However, during liquid metal refining processes, oxygen activity in liquid metal is usually unknown and thus it is impossible to get nitrogen distribution ratio from nitride capacity under this usual condition. In this paper, thermodynamic analysis indicates that the activity coefficient of nitride in slag can be used to measure slag?s ability to remove nitrogen from liquid metal, because nitrogen distribution ratio between slag and metal can be calculated from the activity coefficient of nitride in slag provided that the content of oxygen potential controlling element like Al in liquid metal is available. Review of reported nitrogen removal studies and our recent study has verified that for a given Al content in metal, the lower the AlN activity coefficient in slag is, the higher the nitrogen distribution ratio. Titanium monoxide based slag has been found to be much more effective to remove nitrogen than other slags. Since Al content in liquid metal is usually available during liquid metal refining processes, AlN seems to be a better measure of slag?s ability to remove nitrogen from liquid metal.

Jan 1, 2006

By S. N. Ashrafizadeh

Nowadays, hard carbides have found various industrial application in the manufacture of cutting and drilling tools as well as metal forming devices. About 60% of the world tungsten production is consumed in the manufacture of hard carbide pieces. Regarding the high economic value of hard carbide components, i.e., Ni, Co, TaC, TiC, and WC, their recovery from scrap species is attracting much interest. In the current research, the cobalt and tungsten content were recovered from scrap cemented carbide pieces through the application of high voltage electrolysis in nitric acid media. By this method, cobalt and tungsten were initially recovered as cobalt nitrate and tungstic acid, respectively. The precipitate of tungstic acid was calcined at 800ºC after being washed twice with distilled water. A pure tungstic oxide was obtained. The effects of current density, electrolyte concentration, speed of agitation, and the surface area of the anode on the efficiency of the electrolysis process were investigated. The optimum conditions of current density of 1500 A/m2, an acid concentration of 1.5 M, and a cell temperature in the vicinity of 60 to 80ºC were obtained. At the optimum conditions, an acceptable rate of collapse for the anodic carbide pieces of about 3.1 g/h was achieved, which remained constant up to the completion of the recovery process without any passivation .

Jan 1, 2003

By I. A. Ibrahim

Ilmenite, in its natural form, is an inactive mineral from which the selective removal of iron is rather difficult. The reactivity of ilmenite. so that it can be leached with dilute hydrochloric acid, can be enhanced by chemical reduction in solution using a suitable metal as a reducing agent. The present paper aims at the evaluation of an Egyptian ilmenite ore for the production of synthetic rutile by direct leaching with hydrochloric acid in presence of iron powder. In this process, the titanium and iron contents are dissolved; meanwhile, the dissolved titanium is hydrolyzed and re-precipitated leaving mainly iron in solution. Leaching conditions were optimized to obtain less iron in the final solid product. Addition of sufficient amount of iron powder during leaching reduces the dissolved Fe3+ to Fe2+ and reduces the dissolved Ti4+ to Ti3+. The creation of Ti3+ in solution is assumed to have a role in dissolving the ferric iron and hence increasing the reactivity of the ilmenite ore. Synthetic rutile of about 90% TiO2 and 0.77% Fe2O3 was obtained from ore with a grain size 100% passing 200 mesh and a 5-hour leach time with 20% HCl at boiling temperature (110°C) and 0.11 g iron powder / g ore.

Jan 1, 2003