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By Anastasia Alksnis

Pyrrhotite is an iron deficient, low nickel content sulfide mineral that is commonly associated with pentlandite, a nickel-rich sulfide; and are both main components of the nickel ore mined in Sudbury. Pyrrhotite tailings generated in the concentration of Ni ores are stored in tailing reservoirs and presents serious environmental risks including acid mine drainage. This study investigated the potential of converting pyrrhotite into a valuable resource through the use of fluidized bed roasting, in which the mineral will be oxidized to produce iron oxide and SO2 gas. These products can then be used to create iron for high-grade steel and elemental sulfur. Thermogravimetric analysis of Sudbury pyrrhotite was performed to study the oxidation kinetics, supporting the feasibility of this process. Further, energy and materials balance was carried out to establish the basic parameters of a possible roasting process.

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 S. Lu

The particle-bubble attachment and the rupture of formed aggregates in flotation cell were investigated in terms of turbulent regime. It was found that the particle-bubble collision rate is closely correlated to the energy barrier between particles and bubbles, and no adhesion takes place for the hydrophilic particle-bubble system due to the introduced ?capture efficiency? f(a) being zero. The values of an especially defined Weber number, i.e. the ratios of turbulent stress to aggregate strength in the inertial subrange of turbulence were estimated, the results showed that the detachment of a particle from a bubble involved in an aggregate is mainly caused by the turbulent stress only in the impeller zone, no bubble splitting occurs both in the impeller zone and in the bulk zone.

Jan 1, 1993

By D. J. M. Grodzian

Polymorphic transformations taking place in grinding processes, of massicot to litharge in PbO system, and of y to a in Fe203 system, were re-investigated. Grinding was carried-on in a steeel rotation mill charged with WC balls, under inert atmosphere. The kinetics of transformation in PbO was established by means of quantitative X-ray diffraction analysis. The resulting data fit a modified logistic growth function up to about 75% of transformed volume fraction, when a mixture at steady-state equilibrium is formed. The reasoning for the use of a modified logistic function is discussed. A sigmoidal growth function can be used if resulting data fit also an empirical power relationship between transformed volume fraction and time. However, it lacks the significance expressed by a modified logistic function. Assuming, the loss in magnetism is directly related to the amount of transformation in Fe 203, a quantitative analysis was performed using a magnetic balance method. The results fit only the modified logistic growth function, and transformation proceeds almost to completion. A wide literature survey of the subject is given. Available data from literature is compared with the results of the present study, and is shown also to fit a modified logistic grown function, with surprisingly similar slpes in a linear plot, independently of the material. The instrumentation effect on kinetics parameters, and the establishment of equilibrium mixture values, are discussed.

Jan 1, 1975

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 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

Kinetics of Reclamation of E-Waste by a Bioleaching Route

Sep 13, 2010

By Manoj Kumar, S. Ranganathan, S. N. Sinha

The reducibility of three different manganese ores with coke was studied. The three ores were reduced to different extents under the same experimental conditions. The investigations showed that in the temperature range of 900-1000 ×C, Fe2O3 in the ore was reduced to metallic iron. MnO2 was reduced to Mn3O4 in all cases except one in which it was reduced to Mn2O3. The kinetics of reduction was controlled by different mechanisms in the different ores. Temperature had a significant influence on the reducibility of the ores.

Jan 1, 2007

By B. S. Terry, C. L. Harris

Reduction kinetics from slags containing CuO(0.5), ZnO, PbO, NiO and SnO into a Cu-based metal phase were subjected to computer simulation using a previously developed model for the kinetics of metal-slag-gas reactions that assumes mass-transfer control in all phases. The effects were examined of changing bulk Fe oxide activity, gas reducing potential, temperature, Fe content of the Cu phase and metal/slag ratio. The results permit practical conclusions to be drawn about industrial slag-cleaning practice, but the model is still limited in terms of thermodynamic inputs and the idealisation of reaction conditions

Aug 1, 1995

By B. S. Terry, C. L. Harris

After measuring the kinetics of Ni reduction from a SiO2-saturated fayalite slag into a Cu-based metallic phase on a laboratory scale, a general model was developed that is capable of simulating mass transfer to and from metal-slag, slag-gas and metal-gas interfaces for multiple species. The model was used to simulate the reactions that occur when Cu and Ni are reduced from fayalite-based slags into a Cu-based metallic phase. Good agreement was achieved between model predictions and experimental data

Aug 1, 1995

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

By Omid Marzoughi

In this research, both the kinetics and the mechanisms of the roasting of a sphalerite concentrate from the Bafgh mining complex in Iran were investigated. The oxidation process was performed in a muffle furnace in air and the effects of time and temperature on the degree of oxidation of the zinc sulfide sample were quantitatively studied. The experimental data were fitted to the shrinking core model. In the temperature range of 650–800 °C, the rate-controlling step was the chemical reaction between the zinc sulfide and oxygen with an activation energy of 103 kJ mol−1. On the other hand, in the temperature range of 850–950 °C, the rate-controlling step was oxygen diffusion with an activation energy of 50 kJ mol−1. Also, the roasting process was studied using thermogravimetric (TGA) and derivative thermogravimetric (DTGA) techniques.

By E. Asselin, P. Sauve, H. Salomon-de-Friedberg

"Residues from the CESL Copper process were leached using the CESL Gold process. The kinetics of reaction were confirmed to be fast with over 50% of the gold consistently extracted within 2 minutes of leaching. Final gold extractions under the conditions tested here were between 80-90% obtained within 90 minutes. A model for the CESL Gold process was developed. This model is slightly different based on whether the copper concentrate leach residue was ground or unground prior to leaching: the gold leaching rate constant is approximately twice as fast for the ground samples. Unground residues had a P80 of 13 ?m whereas ground residues had a P80 of 10 ?m. The model predicts a 43% decrease in leaching time for ground residue versus unground residue to achieve the same extraction under otherwise identical conditions. The model was more accurate for the ground samples. INTRODUCTIONTeck's CESL Process (Jones, 1996) was developed to provide an economically attractive alternative to traditional copper smelting. It has since evolved to also deal with copper concentrates containing valuable impurities such as nickel and undesirable ones, such as arsenic, while reducing downstream costs. Effective recovery of gold and silver is essential to the economics of the CESL Process. The Brook Hunt 2007 copper concentrate assay data (Wood-Mackenzie, 2007) were examined to determine the ratio of gold plus silver value relative to the contained copper. As indicated in Figure 1 below, nearly two-thirds of concentrates have 10% or more of their total value tied up in their precious metals content.CESL has extensively examined the recovery of gold and silver at bench, pilot and demonstration scale, which has culminated in the present CESL Gold Process (Barr et al., 2007). The process targets the precious metal contained in the leach residues produced in the copper portion of the flowsheet. This residue has two primary components which influence downstream processing. The major iron-rich fraction (-75 wt%) of the residue is a mixture of various forms of iron oxide precipitates including hematite and jarosite (Sahu and Asselin, 2011). The iron fraction ranges from amorphous to crystalline in nature depending on the compound precipitated, upstream operating conditions and feed material composition. The lesser, but by no means less important, fraction is a mixture of elemental sulphur and unreacted sulphides (principally pyrite).Elemental sulphur formed during the oxidative leach of the copper concentrate reacts with cyanide to form thiocyanate (SCN-) making a traditional cyanide leach approach too costly. Since the SCN formation reaction strongly depends on contact time with the CESL residues (Po, 2007) short contact times were preferred. This factor guided the development work towards the eventual room temperature, pressure cyanidation process which results in near complete gold dissolution in 90 minutes. A recent CESL gold demonstration campaign treating 1.5 t/d of residue from the copper oxidation step achieved an average gold extraction of 91% (96% maximum)."

Jan 1, 2012

By R. B. Anderson

As a part of a Bureau of Mines program on the conversion of coal to liquid and gaseous fuels, the kinetics of the Fischer-Tropsch synthesis on iron catalysts was investigated. Nitrided catalysts were studied at 21.4 atmospheres using feed gases ranging from 2H2+1CO to 0.25H2+1CO, and at 7.8 to 21.4 atmospheres using 1H2+1CO gas. The overall apparent activation energy increased with increasing carbon monoxide content of the feed gas from 19.5 kcal/mole for 2H2+1CO to 23.7 for 0.7H2+1CO. The rate of synthesis with 1H2+1CO feed increased linearly with operating pressure from 7.8 to 21.4 atmospheres. A semifundamental rate equation of the form [r=a'PH2 0.6pco 0.4- ?r0.5PH200.5] was shown to fit the data satisfactorily. The relative usage of hydrogen to carbon monoxide decreased with increasing conversion, passed a minimum, and then increased. Apparently water is the principal primary product and carbon dioxide is produced by subsequent water-gas shift reaction. In another group of experiments water, carbon dioxide, argon, and methane were added to 1H2+1CO feed to a nitrided iron catalyst. Argon and methane were only diluents. Carbon dioxide was a slight inhibitor and water vapor was a strong inhibitor to the rate of synthesis. Water accelerated the water-gas shift and usually increased methane production. Important factors of catalyst geometry in determining rate were found to be particle size and extent of reduction. Apparently the active portion of the catalyst is confined to a layer of 0.01 to 0.02 cm from the external surface of particles. A special solution was made of differential equations relating re¬action at the catalyst surface to diffusion in pores of the catalyst for spherical particles with an active layer surrounding an inert core. The equation derived expressed the experimental data reasonably well. Diffusivities determined by this equation varied from 3 to 24X10-6 cm2/sec; these values are of the same magnitude as observed for the diffusion of gases in liquid. The appendix presents a group of synthesis experiments at pressures of 21.4 to 103 atmospheres. In this range the rate of synthesis on nitrided iron catalysts increased with pressure to the 0.74 to 0.84 power.

Jan 1, 1964

By Matthew Novak, J. Brent Hiskey

It is well known that when chalcopyrite is put in direct contact with copper in an acidic medium a galvanic cell is created. Chalcopyrite is reduced to iron and sulfur deficient defect phases such as bornite, chalcocite, and at very low potentials to elemental copper. Galvanic conversion experiments were performed using three chalcopyrite concentrates. The first chalcopyrite contained less than 10% impurity phases. The second concentrate had a high concentration of pyrite, and the third concentrate had a high concentration of pyrrhotite. The effect of temperature, acid concentration, chalcopyrite grain size, copper grain size, and agitation on the rate of chalcopyrite conversion was studied.

Jan 1, 2014

The widely accepted kinetic model for the gaseous reduction of hematite is critically examined. The formation of the wustite layer during internal reduction cannot be explained in terms of solid-state diffusion. Present evidence indicates the existence of a micropore system in the wustite adjacent to the magnetite with the gas/solid type of reaction occurring not only at the iron/wustite interface but also at the wustite/magnetite interface. During the partial reduction of dense hematite pellets, in a controlled atmosphere, porous magnetite and wustite are formed as products. The mean pore size, as measured by mercury injection, increases with time at constant temperature and with temperature increase over the range 6500C to 950°C. The sizes of the pores indicate that Knudsen diffusion is the principal gaseous transport mechanism across thick layers of magnetite or wustite.The kinetics of the gaseous reduction to iron are consistent with a mixed control mechanism involving the interaction of gaseous diffusion effects with a first order reversible chemical reaction at the iron/wustite interface. Because of the larger pore sizes in the iron layers, ordinary molecular gaseous diffusion must be the principal transport mechanism. The usual experimental methods used for establishing the validity of chemical rate ~ontrol are incapable of differentiating between the mixed control- mechanism and exclusive chemical control.Some implications of mixed control kinetics are developed, including a predicted independence of rate on reducing gas pressure at higher pressures.INTRODUCTIONAn extensive literature review of the reduction of iron oxides has been compiled recently by Themelis and Gauvin (1962). From the large number of papers published and the widely divergent opinions of workers in this field, it appears that a simple unified quantitative analysis of reduction kinetics is not possible. The aim of the present paper is to show that a major cause of confusion is due to the attempts of many workers to interpret experimentally observed reaction rates in terms of a single rate controlling mechanism without due regard to other rate processes which must occur simultaneously.Some of the differences in behaviour reported for particles...

Jan 1, 1964

By J. R. Donald

Electric arc furnace (EAF) dust, which can be considered as a by-product of the steel recycling process, contains significant quantities of recoverable zinc and iron, as well as hazardous elements such as cadmium, lead and chromium, which can be leached by ground water. The zinc in the EAF dust is found almost entirely in the form of either zinc oxide or zinc ferrite, the latter accounting for 20 to 50 percent of the total zinc. It is important that an efficient process be developed which renders the dust inert, while reclaiming the valuable metals to off-set processing costs. During the conventional carbothermic reduction processes, iron is formed, and this iron can participate in the reduction of the zinc oxide in zinc ferrite. In the present work, the reduction of the zinc oxide in zinc ferrite by iron according to the following reaction: ZnO-Fe2O3(s,s) + 2 Fe(s) = Zn(g) + 4 FeO(s) was studied in an argon atmosphere using a thennogravimetric technique. First, a thermodynamic analysis was performed using the F*A*C*T computational system. Then, the effects of briquette aspect ratio (lid), temperature, zinc ferrite particle size, amount of iron added, as well as additions such as lime, sodium chloride, and calcium fluoride were investigated. It was found that, initially, the reaction was chemically controlled with an activation energy of 178.1 kJ/mol. Then, after a product layer had formed on the outer surface of the briquette, the reaction was restricted by the diffusion of zinc gas away from the reaction interface. The parabolic rate law was fitted to the experimental data, and the parabolic rate constant was found to be: = -6.2275 + 0.0054 T (K)

Jan 1, 1995

By Xirneng Zhu

The electrochemical behavior of Pittsburgh and Illinois coal pyrite in basic and neutral borate/sulfate solutions was investigated. In the transpassive region, aggressive oxidation of pyrite occurred. The reaction products in this region were Fe(III) oxide, sulfate ion and partially oxidized sulfur intermediates. The formation of sulfur and polysulfides was identified by in-situ Raman spectroscopy. The growth kinetics of the reaction product film, resulting from transpassive oxidation of coal pyrites, were studied using chronoamperometry measurement with both stationary and rotating disk electrodes. The reaction rate was well correlated by a paralinear rate equation. The effects of electrode rotation speed, solution pH and temperature were examined. The kinetics were compared to those for mineral pyrite.

Jan 1, 1994