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By I. Gaballah

The kinetics of oxychlorination of pure CI-2O3 with C12+02 gas mixtures is studied by ThermoGravimetric Analysis (TGA) in non and isothermal conditions up to 1000 °C. The reaction of Cr2O3 with C12+O2 chlorination gas mixtures starts at about 550 °C and the reaction product is CrO2Cl2. The oxychlorination rate of Cr2O3 is almost proportional to the chlorine partial pressure and to the fourth root of the oxygen partial pressure in the chlorinating gas mixtures. At 800 °C, the maximum chlorination rate is obtained using a gas mixture having a C12/O2 ratio equal to 4. The apparent activation energy of the oxychlorination reaction of Cr2O3 is 87 and 46 kJ/mol at temperatures lower and higher than 650 °C, respectively. By varying the chlorine and the oxygen partial pressures of the oxychlorinating gas mixtures at temperatures higher than 550 °C, it is possible to extract selectively the chromium chlorinated compounds from the chromium bearing materials. a. Laboratoire Environnemem et Minéralurgie, BP 40, 54501 Vandceuvre, France, b. École Nationale Supérieure de Géologie, Rue du Doyen Marcel Rouhault, 54501 Vandoeuvre Cedex, France, c. Centre National de la Recherche Scientifique, 3 rue Michel - Ange, 75794 Paris Cedex, France, d. Insritut National Polytechnigne do Lorraine, Rue de la Font de Haye. 54501 Vandceuvre Cedex, France.

Jan 1, 1997

By Milton Blander

"A review of concepts and theories for predicting thermodynamic solution properties of multicomponent high temperature liquid solutions is reviewed. During the last 50 years the ability to predict such properties for molten salts, silicates and metals based on the generally known properties of the lower order (often binary) systems has been developed and shown to provide predictions which are quite useful in science and technology. There are many gaps in our understanding of these high temperature solutions, especially for metals, and considerably more work is needed.INTRODUCTIONA number of solution theories and concepts have been developed which reliably predict the properties of multicomponent solutions from those of the lower order systems (often only the binaries). Because there is available data for a large fraction of the important binaries, the capability for making predictions for many multicomponent systems used in metallurgical separation processes is broad and potentially very useful. At the very least, the theories greatly minimize the data necessary for predicting properties of complex multicomponent solutions of molten salts, silicates and metals. It is the purpose of this paper to discuss the concepts which are demonstrably useful. We will discuss simple forms of the theories to make the concepts clear but we will refer to the publications which contain the more complex equations needed to treat the large majority of systems.A simple framework for understanding what we need to know in order to make technologically useful predictions is based on well known thermodynamic principles. In technologies and sciences where molten salts, slags magmas or molten metals are used or studied, one must often calculate the extent of a chemical reaction (or separation) or of phase changes. To do this, one must first write an equilibrium constant, K, for the reaction in terms of the standard free energy change of the reaction, ?G°."

Jan 1, 1996

"Mixing phenomena in a bottom blown air-stirred one-seventh water model of CLU (Creusot-Loire Uddeholm) reactor was studie9-using three different configurations of straight circular nozzles fitted axially at the bottom of the vessel. The mixing time has been determined by pH measurements at various gas flow rates, bath heights and nozzle orientations in the presence and in the absence of a second phase.Experimental results reveal that the mixing time decreases with increasing gas flow rate. For a given gas flow rate the mixing time increases non-linearly with increasing bath height. Off-center configuration gives slightly lower mixing times as compared to center configuration. It is found that the contribution of buoyancy to the total stirring energy density is very small, but its contribution increases with increasing bath height. In the presence of an upper oil layer, the mixing time increases significantly for all configurations.IntroductionIn high temperature metallurgical melts mixing is carried out by injection of a gas either from top or bottom of the vessel in order to accelerate the rates of chemical reactions and to promote bath homogenization. When a gas is injected into a liquid through a submerged lance, porous plug or nozzle, the gas, rising as a two phase plume to the surface, imparts momentum to the surrounding liquid and causes gross circulation in the bath which promotes mixing."

Jan 1, 1997

By Fujio Ishii

The deoxidation of liquid nickel and nickel binary alloys with silicon has been determined at temperatures between 1500°C and 1650°C using quartz crucibles in order to investigate the deoxidation of nickel based alloys. The equilibrium constant of the deoxidation reaction in liquid nickel and the effects of the different alloying elements such as chromium, molybdenum, tungsten, iron, cobalt and coppcr on the activity coefficient of oxygen in liquid nickel have been established.

Jan 1, 1993

By Faustino G. Prado

In the, quest for an economical and environmentally friendly reclamation of metallurgical dusts generated during pyrometallurgical operations, our goal has been the separation and recovery of most of the components, as well as the complete recycle of all the reagents. Effluents have been avoided, within acceptable economic parameters. This presentation, which can be applied to a large spectrum of dusts and other residual-materials-, has focused on the dusts generated by the operation of Secondary Copper Smelters. Those dusts show a wide range of components, including zinc, lead-, copper, cadmium, tin, chlorine and-alkalies. Our present work deals with the use of ammonium salts in the separation and recovery of-the above mentioned elements in a marketable form. Most of the chemistry and techniques involved have teen already confirmed in commercial scale operations. Others have gone through pilot scale tests or bench scale tests. The recycle of reagents has also been- confirmed at the same operating levels. A preliminary evaluation indicates that the chosen route, in addition to a viable economy, offers a complete and safe reclamation within the most strict environmental regulations.

Jan 1, 1995

Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

By Gordon Lewis

A complex mixture of hydrated reaction products is obtained from hydrothermally treated refractory cements and castable concretes. TGA can be used both to identify the product phases in the mixture and to determine a quantitative relationship among the phases. When reacted mixtures contain compounds that decompose simultaneously, or nearly so, additional assumptions must be introduced in order to develop a quantitative phase analysis. It is the purpose of this paper to examine some of these assumptions and to demonstrate their application, particularly to refractory cement systems.

Jan 1, 1982

By F. Patisson

During exothermic gas-solid reactions, heat generation makes temperature rise and modifies the rate of the various mass transfer processes, namely the chemical reaction itself, the pore diffusion and the external transfer. We have investigated this thermal effect during the oxidation of zinc sulfide porous pellets in a thermo balance furnace, between 550 and 900°C-and under O2-N2 atmosphere. The results have been' analyzed by using, firstly, the law of additive reaction times derived from the isothermal Grainy Pellet Model, and, secondly, a new numerical model taking into account non-isothermal conditions. Both the models can satisfactorily simulate conversion versus time, but the numerical model also depicts the temperature evolution within the pellet. Finally it is shown that owing to the heat generation the zinc sulfide oxidation takes place under diffusion control (3/4 internal, 114 external) in all the cases studied. During the course of reaction, the. pellet undergoes strong temperature variations, with thermal gradients confined to a shell oxide layer.

Jan 1, 1996

By Shengqi Chen

The reduction smelting of nickel laterites produces slag, consisting principally of the chemical components MgO, "FeO", SiO2, and A12O3, and ferro-nickel alloy. Despite the fact that the phase equilibria for the ternary MgO-"FeO"-SiO2 up to 1500°C is well established limited experimental data are available in the MgO-"FeO"-SiO2-Al2O3 system, which is relevant to commercial operation of the process. A methodology has been developed for the experimental investigation of the liquidus temperatures for the multi-component system MgO-"FeO"-SiO2-Al2O3-Cr2O3 in equilibrium with metallic iron. Experiments have been carried out using high temperature equilibration, quenching, followed by electron probe X-ray microanalysis (EPMA). Liquidus temperatures have been determined in the silica primary phase field in the composition ranges directly relevant to the Cerro Matoso S.A. ferro-nickel smelting slag. Liquidus isotherms have been determined for temperatures between 1450 to 1600°C. The study enables the liquidus to be described for a range of MgO/FeO ratios. It was found that liquidus temperatures in the silica primary phase field decrease significantly with the addition of AI2O3. Keywords: Liquidus temperature, ferro-nickel, pyrometallurgy, smelting

Jan 1, 2004

By E. Oshima

In May 1991, a New Mitsubishi Continuous Copper Smelter Line started operation at Naoshima. Recently, it has been continuing steady operation and one and a half year campaign life has been achieved. In 1996, new records of on line time, the amount of copper concentrate treated and copper anode production were achieved. 1t proves the superiority of the process with respect to pollution control, energy efficiency, flexibility and easiness of the operation and over all economy including off gas handling cost. Furthermore, .plans are underway to prolong the campaign life for two years and to improve the process efficiency. This paper describes recent operation, improvements, and a future capability study.

Jan 1, 1998

By Bin Xu, Qian Li, Yong-bin Yang, Tao Jiang, Jian-jun Hu

It could significantly increase the leaching rate of refractory gold concentrate containing sulfur and arsenic by roasting pretreatment with adding certain amount of sodium sulfate, and the mechanism of that was systematically researched with DSC, XRD and SEM in this paper. Results indicated that the mechanism of Na2SO4 on double refractory gold concentrate at roasting pretreatment can be summed up in the following three aspects：Firstly, Na2SO4 can react with SO2 and SO3 which is produced by the oxidation of sulfides and generate Na2S2O7(l), which plays buffer effect on sulfides exothermic oxidation, avoiding the secondary-encapsulated of gold. Secondly, the liquid phase of Na2S2O7 can cover mineral particles' surface that possesses a sintering effect, it leads to internal cracks of the particles. Finally, mineral particles will gather with sodium sulfate particles as the center that can improve the permeability of the layer.

Jan 1, 2015

By Randall M. Gennan

Generally sintering is focused on the bonding of particles at high temperatures; possibly with simultaneous densification. However, an important aspect of sintering occurs during heating at relatively low temperatures where polymer processing aids are removed via control of the atmosphere, heating rate, or hold time at intennediate temperatures. New insights into burnout processes show impact from the polymenype, particle size, amount of polymer, atmosphere, part geometry, and thermal profile. This presentation focuses on the key parameters to demonstrate improved mechanical property levels are available in traditional powder metallurgy alloys by proper selection of the processing polymer and proper care in its thermal extraction. The focus is on mechanical property, where gains up to 40% are demonstrated due 10 changes in the processing polymer. Further, atmosphere control during polymer burnout provides a benefit by allowing formation of desirable carbonitrides, giving strength levels over 3 GPa (over 400 kpsi). Insight is? gleaned from powder injection molding, where high polymer contents mandate proper processing control.

Jan 1, 1996

By Frederick W. DeVries

The author was invited by "60 Minutes Australia" to provide on-site technical background on cyanide, mining, and the environment, in their investigation of the January 30, 2000, spill at the Aurul gold-recovery site in Baia Mare, Romania. Some remarks on the incident ?and its implications surround a showing of the fourteen-minute telecast. The thrust of the TV reporter was that aspects of the dam implied the owners' use of standards Jess than would have been met for installations in technologically more advanced locations (like Australia). As a result, the public-relations impact is one of embarrassment for the world mining industry.

Jan 1, 1998

By S. N. Sinha

The distribution coefficients of lead and silver between copper and matte phases have been measured at two different temperatures. Experiments covered the ranges of 0.009-1.8, 0.07-0.13, and 0-11 wt pct lead, silver, and iron in matte, respectively. The distribution coefficients of lead have been measured at 1405 and 1505 K and correlated with lead and iron concentrations in metallic copper and matte. The values of the distribution coef¬ficient of lead between copper and iron-free matte, at infinite dilution of lead, have been determined to be 3.60 and 4,06 at 1505 and 1405 K, respectively. The distribution coefficient of silver between copper and iron-free matte is independent of silver concentrations and has been measured to be 2.13 and 2.21 at 1400 and 1500 K, respectively. For an iron-bearing matte, the distribution coefficient of silver has been correlated with iron concentration in the matte at both 1400 and 1500 K. From the measured values of distribution coefficients, the Raoultian activity coefficients of PbS and AgS0.5 in copper-saturated matte have been calculated. At infinite dilution, the following equations correlating the Raoultian activity coeffici¬ents of PbS and AgS0.5 with matte- composition and temperature have been obtained: log Y° PbS =1.515 + 1080/T 0.14 NFes lbS Fog YAgS = -0.074 - 425/T + 0.09 NFes. - 0.5

Jan 1, 1983

By Gaballah I.

Elimination of arsenic, mercury and zinc from synthetic solutions containing H;\A.sD4. HgCI2 and ZnCI2 using modified barks was investigated. The pH range was varied from ?1 to 10. The initial concentrations of individual element were 10,100 and 1000 ppm. More than 99 % of mercury and 65 % of zinc cations were removed by the modified bark .. In this case, the modified bark reacts as a cation exchanger leading to the release of ' two protons for every HgII or ZnII fixed by this material. About 30 % of arsenic was eliminated from the solution. This 'low efficiency could be attributed to? the presence of arsenic ,as. anion. Decontamination of a treated industrial effluent containing 4 ppm of ion? metals was performed on a pilot plant scale by the modified bll(k. More than 70'% of these ion metals were eliminated.

Jan 1, 1995

By Kimio Itagaki

"As a contribution to understand the smelting of copper or nickel matte by blowing oxygen or oxygen-enriched air, the phase equilibrium and the distribution of minor elements between the iron-silicate based slag and the Cu2S-FeS or Ni3S2-FeS matte at 1573K were investigated in a magnesia crucible under controlled partial pressures of SO2 at 0.1, 0.5 and 1.atm. At a given matte grade, the solubility of copper in the slag was found to be independent of p5O2 while that of nickel was dependent on pSO2 and these behaviors were analysed thermodynainically based on a concept of oxidic and sulfidic dissolution of the components in the slag. When the matte grade was specified, the distribution ratios of X, defined as (wt pct X in slag)/(wt pct X in matte}, for As, Sb and Bi increased with increasing p5O2 while that for Ag was constant against p5O2.IntroductionA combination of intensive reactors with the use of oxygen or oxygen-.enriched air as the blowing gas has provided a number of improved copper and nickel smelting processes such as INCO-Flash, Outokumpu-Flash, Mitsubishi-Continuous and IBRC (top blown rotary converter) processes. Phase equilibrium and thermodynamic studies for the slag and the copper matte or the nickel matte under high partial pressure of SO2 are of practical importance for evaluating the behaviours of the related components in the oxygen-smelting.A series of experimental studies have been already conducted in a limited range of conditions for Pso2 around 0.1 atm, which corresponds to the smelting with air-Stowing [1-5]. However, there remain very few data on the phase equilibrium in the matteslag systems under higher partial pressures of SO2. Tavera and Davenport studied the phase equilibrium between the copper matte and fayalite slag phases under the partial pressure of SO2 controlled at 0.1 - 1 atrn but without controlling the partial pressures of sulfur and oxygen [6]. A potential diagram for the Cu-Fe-S-O-SiO2 system at 1523 - 1573K suggests that the partial pressure of S2 equilibrated with the matte and the fayalite slag with saturated SiO2 under the high SO2 pressure is considerably high at 10-4 - 10-2 atrn [7]. This condition must require controlling of p52 as well as Pso2, in the equilibrium experiments, otherwise, the equilibrium condition may be hardly attained due to the continuous flushing of sulfur from the system."

Jan 1, 2000

By Qinmeng Wang

The oxygen bottom blown copper smelting process is a new technology which has been widely applied to the copper production in China. In this work, a computational thermodynamics model for this technology has been established, based on smelting mechanism and theory of Gibbs free energy minimization. The calculated results from the model agree well with the actual industrial data, indicating that the model can be used for the predictions under different operating conditions. The tendencies of the key parameters (such as Cu losses and Fe3O4 content in slag) and the distribution ratios of the minor elements (such as Pb, Zn, As, Sb and Bi) can be predicted by adjusting the oxygen/ore ratio charged into the bottom blown copper smelting furnace. The model can be used to monitor and optimize the industrial operations of the oxygen bottom blown copper smelting process.

By J. H. Huang

In this investigation, the selective precipitation of cobalt and molybdenum from Co-Mo aqueous solutions was studied in order to recover efficiently valuable elements from industrial effluents generated from a novel electrodeposition of nanocrystalline Co-based alloys process and reduce the effluent impact on environment. It was found that the behavior of cobalt in aqueous solutions was substantially affected by the presence of molybdenum. When adding 11.6 to 46.6g/L molybdenum to a 50g/L cobalt solution, the co-precipitation of molybdenum and cobalt started to occur at pH value of 3-4. However, without the presence of molybdenum, cobalt could only be precipitated out of the solution at about pH 6. Most of the molybdenum was found in the solid phase when the solution pH reached 5. After further increasing pH to greater than 7, the molybdenum dissolved back into the solution. Cobalt kept precipitating as the pH increased. When the pH was greater than 7, most of the cobalt was present in the solid phase. The chemical and physical characteristics of the precipitated materials were investigated by SEM, XRD, AAS and EDX. It was revealed that the precipitate was initially present as cobalt molybdate oxide hydrate and subsequently transformed as sodium cobalt molybdenum oxide. With further increasing the solution pH, the precipitate was transformed into cobalt hydroxide. Further investigation implied that most of molybdenum was chemically tied to the precipitate produced at the low pH, yet at the same time, physically entrapped at the high pH. The paper also presents the influence of reaction temperature and time on the precipitation process and kinetics.

Jan 1, 2003

By M. C. Esposito

Seven pyrite samples purified from coal sources and one ore source pyrite (for comparative purposes) have been characterized by chemical and mineralogical analyses, inherent floatability, apparent specific gravity, surface area, semiconductor type, optical anisotropy, dissolution and oxidation rate. The data clearly demonstrate that pyrites from various coal sources differ not only from ore pyrite but from each other as well.

Jan 1, 1987

By J. D. Law

The presence of long-lived radionuclides presents a challenge to the management of radioactive wastes. Separation of the radionuclides from the waste solutions has the potential of significantly decreasing the costs associated with the immobilization and disposal of the waste by minimizing waste volumes. Several solvent extraction processes have been developed at the Idaho National Engineering and Environmental Laboratory for the separation of transuranic elements (TRUs), 90 Sr, and/or 137 Cs from acidic radioactive waste solutions. The TRUEX and POR processes for the separation of TRUs, the SREX process for the separation of 90Sr, the cobalt dicarbollide process for the separation of 137Cs and and a universal solvent extraction process for the simultaneous separation of TRUs, 90Sr, and 137Cs have all been developed in centrifugal contactors using actual liquid radioactive waste solutions and simulated dissolved calcine waste solution. In addition, the behavior of metals with each of the solvent extraction processes was evaluated. This article summarizes the most recent results of the each of the flowsheet demonstrations and provides Information on the centrifugal contactor equipment used for the testing.

Jan 1, 1999