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By Harrison Hodge

In the Bayer process for alumina production, between 2–35% Al2O3 is lost with bauxite residue due primarily to incomplete dissolution of aluminiumbearing minerals during caustic leaching or the precipitation of sodium alumino-silicate solids. The recovery of sodium and aluminium from the residue, and particularly from the contained sodium alumino-silicates, is becoming an increasingly critical issue from both an environmental and economic standpoint. Lime-soda residue sintering followed by selective leaching has been proposed as a method to recover sodium and alumina. The factors influencing the sintering mechanisms and kinetics, and the subsequent leaching have not been well described to date. In this study, the physical and chemical changes taking place during isothermal sintering of bauxite residue in air, particularly at short reaction times are investigated using scanning electron microscope (SEM) and X-ray diffraction (XRD). The impacts of these changes on the recovery of valuable materials are reported.

By N. Kanari

Kinetics of the carbochlorination of Cr2O3 has been studied with C12+CO gas mixtures between 500 °C to 900 °C using thermogravimetric analysis. The apparent activation energy is about 100 kJ/mol. Mathematical fitting of the experimental data suggests that the shrinking sphere model is the most adequate to describe the carbochlorination mechanism of chromium oxide and that is controlled by the chemical reaction. In the temperature range of 550 "C to 800 OC, the reaction order is about 1.34 and is independent of temperature. Changing the C12+CO content from 15 pct to 100 pct increases the reaction rate and does not affect the reaction mechanism. Similarly, changing the ratio of C12/(Cl2+CO) from 0.125 to 0.857 do not modify the carbochlorination mechanism of Cr203. In these conditions, the reaction rate passes through a maximum when using a chlorinating gas mixture having a Cl2/(C12+CO) ratio of about 0.5.

Jan 1, 1998

By J. Diao

In order to understand the flotation kinetic behavior of coal and associated mineral matter, a detailed investigation was conducted in a 2-liter Denver flotation cell using three high sulfur coals at three feed sizes, minus 28. 100 and 200 mesh. Subsequently. the flotation products were sieved into different size fractions and analyzed for their ash and pyritic sulfur content in order to delineate the effect of particle size on the rate at which each constituent floats. The results were tested with several different flotation kinetic models and the best model for coal was then chosen. The flotation rate constant and the ultimate recovery calculated from a kinetic model were used to delineate the effect of particle size, collector (dodecane) and frother (MIBC) dosages on the flotation kinetics of coal, ash and pyrite.

Jan 1, 1992

By A Holmgren, W Forsling

In the present study infrared attenuated total reflection (IR-ATR) was used to monitor the rate of in situ adsorption of heptyl xanthate on a layer of zinc sulfide synthesised on a germanium ATR crystal. The zinc sulfide surface was characterised using x-ray photoelectron spectroscopy (XPS). The absorbance of heptyl xanthate measured increased with increasing bulk concentration of the adsorbate up to an equilibrium plateau value corresponding to a fractional coverage of the surface sites of the substrate. For the adsorption from solutions of concentrations between 10-3 and 10-5 M, the rate of adsorption increased with increasing bulk concentration. At higher concentrations the measured absorbance should be corrected for the absorbance due to the concentration of xanthate in bulk solution. The present work provides a discussion of this correction. Assuming the adsorption stage to be rate-controlling and proportional both to the concentration of the adsorbing species in solution and unreacted surface area, a rate law governing this type of transient adsorption kinetics was derived. By means of absorbance data for the concentrations 0.1 and 0.01 mM, the rate constant of adsorption was calculated. From the initial part of a Langmuir adsorption isotherm, the absorbance at monolayer coverage and the equilibrium constant of adsorption could be estimated.

Jan 1, 2005

By Milorad Cirkovic

Kinetics of copper concentrate oxidation in roasting processes in a fluidized bed reactor has been studied at temperatures between 600°C and 720°C using particles of 0.038 to 2.5 mm in average size. The analysis of composition of samples has been done by chemical methods. Phase composition has been determined by Siemens X-ray equipment with Cu anticathode and Ni filters at a voltage of 40 kV and a current of 18 mA. The content of sulphur has decreased from 33.23 to 19.02 mass percent with the increase of temperature, but the content of Fe304 has increased from 0.15 to 17.14 mass percent. The new mechanism of copper concentrate oxidation in a fluidized bed reactor is proposed in this study. It has been shown from the mathematical model that the velocity of oxidation of copper concentrate between 600°C and 720°C is virtually controlled by the rate of diffusion of 02 through the layer of reaction product.

Jan 1, 1999

By S. P. Mishra, G. R. Chaudhury

The adsorption of Cu2+ ions by Penicillium sp. displayed a dual rate, with an initial faster phase followed by a slower one. The adsorption rate increased with increasing pH due to chemical and biochemical reactions. The Cu-loading capacity of the biomass increased at higher initial Cu2+ concentrations. Above 40 degrees C the adsorption rate decreased which may be due to partial hydrolysis of biopolymers which are essential constituents of the cell wall. Adsorption kinetics followed the Freundlich isotherm and the equilibrium concentration that was calculated on the basis of the isotherm matched the observed value well. A series of theoretical adsorption curves were produced using mathematical correlations between the mass transfer coefficient, the Cu2+ ion concentration at equilibrium and at time t. The correlation between the theoretical and observed adsorption rates for different experimental conditions was good. It was concluded that the results from the study were best explained using a mass-transfer adsorption model

Aug 1, 1995

By X Dai

This paper investigated the loss of cyanide via oxidation in CIP or CIL processes by relating the cyanide oxidation to its major oxidation product, cyanate. The results showed that the oxidation of both free cyanide and copper cyanide complexes are substantially enhanced by the presence of carbon. The rate of cyanide oxidation was found to occur in the order: Cu(CN)32- > CN- > Cu(CN)2-. The cyanide oxidation rate in the presence of copper and carbon increased significantly with increasing dissolved oxygen concentration, typical of CIL vs. CIP conditions. Cyanide oxidation rate of iron, zinc or nickel cyanide complexes was minimal.

Jan 1, 2011

By Rashmi Kumar, Amit Chatterjee, Sanjay Chandra

The practice of adding alloying materials to a molten bath is an integral feature of many pyrometallurgical operations. However, very little is known about the dissolution rate and solution mechanisms of solid additives in liquid melts. In foundries where large tonnages of liquid metals are handled, there is considerable interest in achieving optimum metal quality at minimum cost. This objective is influenced by several factors and the solution is often plant specific. Though the amount, sequence and mode of ferroalloy addition vary from plant to plant, various fundamental factors determine how quickly these additions dissolve in the bath. At the Ingot Mould Foundry (IMF) in TATA STEEL blast furnace hot metal is used to cast ingot moulds. The composition of hot metal desired for making ingot moulds demands addition of 20 kg each of Ferromanganese and Ferrosilicon in the 12 T transfer ladles into which the blast furnace metal is poured at the IMF. Owing to low temperature of hot metal at the IMF, casting commences immediately and complete dissolution of the ferroalloys is often not possible. To study this aspect in detail and to evolve suitable corrective measures, a mathematical model for the melting of a solid particle in a liquid metal bath was developed at TATA STEEL. The model was validated using the data available in literature. In keeping with published work, two separate dissolution periods were identified - a "shell period" and a "free dissolution period". The maximum thickness of the crust formed around a spherical particle shortly after immersion, can be obtained by using the mathematical model which has been developed. The model can also be used to investigate the effect of various parameters such as superheat of the bath, size of the particle, etc., on the maximum crust thickness and the particle melting time. On the basis of this study, the addition of ferromanganese and ferrosilicon was optimized at the IMF in Tata Steel.

Jan 1, 1996

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 Mn304) 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 Mn304 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 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 Bo Björkman

Four different arsenic containing dusts from the Boliden plant, Boliden mineral AB, Sweden have been examined. A kinetic study of the As elimination was performed in a laboratory scale roasting furnace for roasting furnace ESP dust and smelting furnace ESP dust. Characterisation and thermodynamic calculations were carried out to determine the mineralogy, and the stability of compounds in the dusts studied. The characterisation methods used were chemical analysis, X-ray diffraction analysis and microprobe analysis. It was found in the experiments that a high degree of As elimination was obtained for roasting fumace ESP dust and a low degree for smelting fumace ESP dust. Derived kinetic models are given. A prediction of the As-elimation for settling furnace dust and converter ventilation dust is presented.

Jan 1, 1994

By D. S. Flett

Abstract. The commercial importance of hydroxyoximes as extractants for copper has given impetus to basic studies on the chemistry of metal extraction by these compounds. The discovery of accelerator compounds which produce catalytic effects on hydroxyoxime extraction rates has led to mechanistic studies of these rate processes. While these studies have highlighted the importance of interfacial chemical reactions in the extraction process, it is not yet possible to unambiguously describe the mechanisms of metal extraction in these systems or the associated catalytic effects. This paper reviews progress in understanding the mechanism of metal extraction by hydroxyoximes.

Jan 1, 1979

By K. Sasaki, W. Astuti, N. Okibe, T. Hirajima

"The kinetics of leaching of a saprolitic ore from Indonesia by citric acid solution under atmospheric pressure was investigated. An examination of the effects of leaching temperature, citric acid concentration, pulp density and ore particle size on the dissolution rate of nickel found that they all had significant influence on the rate. The highest nickel recovery (95.6 percent) was achieved under the leaching conditions of ore particle size of 212-355 microns, citric acid concentration of 1 M, leaching time of 15 days, pulp density of 20 weight/volume percent, leaching temperature of 40°C and shaker speed of 200 rpm. The shrinking core model was found to be appropriate for describing the leaching kinetics of this ore in citric acid solutions at atmospheric pressure. The experimental data were well interpreted by this model with rate of reaction controlled by diffusion through the solid product layer. Using the Arrhenius expression, the apparent activation energy for nickel dissolution was evaluated as 12.38 kJ/mol. Finally, on the basis of the shrinking core model, a proposed empirical kinetic model for the leaching of nickel from this Indonesian saprolitic ore was expressed as a mathematical model, which was verified as consistent with the observed experimental results.IntroductionIndonesia has some of the world’s largest nickel laterite reserves and was the largest producer of nickel – in the form of nickel lateritic ores – in the world in 2013 (Merchant Research and Consulting Ltd, 2014). However, only high-grade saprolites are processed in Indonesia using pyrometallurgical methods to produce ferronickel and nickel matte. Lower-grade saprolites and limonites are removed, becoming waste or overburden in mining site areas. Hydrometallurgical methods, involving either chemical leaching or bioleaching, are now seen as the most important technologies for treating nickel laterites in the future because of their advantage of not only extracting nickel and iron but also other valuable elements. In addition, hydrometallurgical methods consume less energy and have lower capital and operational costs. Although they are recognized to be more suited to limonites, some researchers have studied their use in the extraction of nickel and other metals from saprolites (Guo et al., 2009; Lu et al., 2013). Hydrometallurgical processes for the extraction of metals, especially nickel, promise to be meaningful alternatives to pyrometallurgical processes to primarily treat low-grade saprolites for which pyrometallurgical processing is not favorable"

Jan 1, 2015

By M. D. Gibbs, T. N. Smith, B. Verbaan

When heated in the absence of oxygen, pyrite from refractory gold concentrates decomposes endothermically to pyrrhotite, releasing sulphur. The decomposition starts at the particle surface and progresses inwards, leaving an adhering layer of porous pyrrhotite. Use of the conventional shrinking-core model implicitly assumes a negligible partial pressure of sulphur in the bed, but this pressure is in fact at least equal to the equilibrium vapour pressure of sulphur over pyrite, constituting the principal control of the rate of decomposition. Further experiments showed a decrease in reaction rate as the conversion increased. Both phenomena are attributed to the persistence of non-isothermal conditions in the fluidised bed during pyrolysis, caused by the endothermic nature of the reaction and the relatively slow rates of heat transfer to particles and vapour removal from the bed. Equipment must be developed to maximise these two parameters

Jun 19, 1905

By S. Chander

The formation of surface films on pyrite has been studied through electrochemical techniques of cyclic voltametry and AC impedance measurements. The characteristics of the surface films depend upon the conditions of oxidation and the source of pyrite. At potentials near 0.0 V, some pyrites have large values of polarization resistance showing a certain degree of passivity. Some pyrites show more passivation than the others, however. On oxidation, metastable phases of Fe(OH2) and Fe(OH3) form which transform to more stable 3 phases on aging. The growth of surface films near the corrosion potential of pyrite follows a linear kinetics which is attributed to a chemical (or an electrochemical) reaction as the rate determining step. The surface film is considered to be a hydroxide or an oxide rather than sulfur because the later is expected to be limited to a monolayer in alkaline solutions. This study has also demonstrated that AC impedance measurements can be used to study the growth characteristics of films at mineral/ solution interfaces.

Jan 1, 1987

By J. A. Arias

The oxidation kinetics of pyrite and refractory gold concentrates in acidified ferrous sulfate solutions in the presence of oxygen-sulfur dioxide gas mixtures has been studied. The effect of temperature, pulp density and gas composition were determined. The optimum oxidation rate was obtained at 80°C and 2 percent sulfur dioxide in the gas mixture. The oxidation of the sulfide minerals is attributed to the presence of ferric ions, which are continuously regenerated by the gas mixture. The objective of this study is to find a new hydrometallurgical method to render sulfidic refractory gold ores amenable to cyanization.

Jan 1, 1993

By Kenneth S. Coley, Michael Pomeroy, Elaine Chen

Recent work on modeling of BOF steelmaking is reviewed, highlighting the critical aspects of each approach. It is concluded that the most successful models should be based on a deep understanding of the mechanisms and kinetics of the critical reactions. The importance of the decarburization mechanism is discussed with particular reference to its role in droplet swelling or bloating which has a profound influence on the droplet residence time in the slag. Conditions which cause bloating are discussed and the rate determining step is proposed to be primarily nucleation of CO bubbles inside the metal droplet with some influence from growth by reaction at the bubble/metal interface. The discrepancy in the super-saturation ratio required for classical nucleation is discussed and an approach using a surface tension modifying parameter is illustrated. Finally, the role of CO nucleation in controlling the driving force for dephosphorization is discussed.

Jan 1, 2014

By Marcelo B. Mourão

An experimental investigation was carried out to -study the rates of reduction of pellets containing iron oxides by carbon dissolved in liquid iron, at temperatures ranging from 1720 K to 1973 K. Several different pellet types were employed; the materials used in the pellet's manufacture were pure hematite, two kinds of commercial iron ores, and mixtures hematite/silica and hematite/lime: Reaction times were determined employing the constant volume pressure increase technique (CVPI). It has been observed that the reaction rate increases as the temperature and the pellet's specific surface area increases. The reaction rate is also affected by the oxide type: pellets made from commercial ores or from mixtures hematite/silica or hematite/lime show reaction rates lower than those made from pure hematite.

Jan 1, 1996

By Vincent Canaguier

Methane is increasingly considered as a promising reductant for metal oxides, including chromite. To assess the possibilities of such reduction route, the gas-solid reactions between Ar–CH4–H2 gas mixtures and synthetic chromites are studied between 950 and 1050 °C. The influence of Mg and Al additions on the reduction-caburization of (Fe,Mg)(Cr,Al)2O4 solid solution is investigated thermodynamically, structurally and kinetically. The product phases are examined by x-ray diffraction (XRD), scanning electron microscopy (SEM), and electron probe microanalysis (EPMA). The reaction rate is derived from real-time exhaust gas measurements and post-reaction product analyses such as oxygen analysis. Kinetic models are proposed based on the product phase morphologies and confronted with the empirical data.

By C. Dorfling

Experimental work was performed using a bench scale autoclave to evaluate the effects that leaching temperature, pressure, initial acid concentration, and the solid to liquid ratio have on the behaviour of base metals and platinum group metals in a high-pressure sulphuric acid oxygen leaching system. The concentrations of metals in the leach solution were measured over time at different leaching conditions. At the conditions investigated, the initial acid concentration had the largest influence on the copper leaching kinetics, while the leaching rates of the other precious metals (OPMs: rhodium, ruthenium, and iridium) were highly dependent on the leaching temperature. A set of chemical reactions that can be used to describe the leaching chemistry was proposed, and the associated reaction kinetics were quantified. As a first estimation, the rate expressions were considered first order, and the rate constants were determined using the method of least squares, considering the experimental and predicted concentrations obtained for the different leaching conditions. Of the OPM compounds, the sulphides showed the fastest dissolution rate, followed by OPM alloys, and finally the OPM oxides. During the initial leaching stages, base metals and OPMs competed for the available dissolved oxygen, with oxygen being preferentially used for copper leaching. Precipitation of OPMs during the initial leaching stages can be ascribed to copper and nickel dissolution according to exchange reactions between dissolved OPMs and copper present as digenite or nickel present as polydymite. Control of the autoclave residence time is of particular importance to enhance the selectivity of this leaching step, given the dependence of the PGM leaching rates on the extent of copper dissolution.

Sep 1, 2012