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By Kezhuan Gu

Data on the kinetics and thermodynamics of dephosphorization are analyzed in terms of the dynamic partition ratio, determined by a combination of slag thermodynamic properties and the balance of oxygen supply and consumption. A recently developed phosphate capacity correlation is combined with data on kinetics to quantify the most significant parameters in controlling the interfacial oxygen potential. The role of slag composition, entrained gas fraction and temperature are discussed in addition to metal carbon and sulfur content. It is demonstrated that the mass transport of oxygen in the slag is enhanced by factors increasing conductivity and inhibited by entrained gas. The mass transfer of phosphorus in the metal is described considering surface renewal induced by CO bubbles.

By M. Sinirkaya

The dissolution process of phosphate rock from the Semikan area (Mardin-Mazidagi, Turkey) using dilute phosphoric acid has been investigated. The work involved studying the effect of important variables, such as reaction time, stirring speed, particle size fraction, phosphoric acid concentration and temperature. Van der Sluis et al.?s model was used to determine the rate of the partial dissolution of phosphate ore. Mass-transfer coefficients (kL) varied between 2.8 and 28.5.10-3 m.s-1. The activation energy of the process varied between 16 and 20 kJ.mol-1. It has been found that the dissolution process is controlled by calcium ion diffusion, rather than by chemical reaction.

Jan 1, 2010

By Shengfan Zhou, XUEWEN WANG, Bianfang Chen, Mingyu Wang

Vanadium was leached from roasted stone coal by NaOH solution, and the effect of leaching temperature, leaching time, addition of NaOH, liquid to solid ratio, the grinding fineness of stone coal, and stirring speed on the vanadium leaching rate was studied. The kinetics analysis for the process is presented by the shrinking core model. The results show that the vanadium leaching ratio of roasted stone coal can be beyond 75% at the 6% NaOH addition, leaching temperature of 95°C, leaching time of 7h, liquid to solid ratio of 1.2mL/g, and grinding fineness of 0.111mm. The leaching process is controlled by interfacial reaction kinetics and the apparent activation energy was 59.36kJ/mol.

Jan 1, 2016

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 S. Joshi, E. Asselin

An electrochemical quartz crystal microbalance (EQCM) was used to study the leaching of pure gold in deaerated 1 M Na2S solution. Multiple cyclic voltammograms were measured between -0.76 and 1.242 V (SHE) at 20 mV/sec and 2 mV/sec and the frequency shift of the quartz crystal was simultaneously measured. Both the forward and reverse scans showed oxidation occurred between -0.40 to 0.20V. The frequency shift increased during both the forward and reverse scans in the potential range of -0.40 to -0.06 V indicating electrode mass decreased. Since at -0.40 to 0.20 V oxidation peaks were also observed, part of the oxidation was due to oxidation of gold. Eh-pH diagrams were constructed and showed soluble Au(I)-S(IV) species formed between -0.30 and 0.10 V (SHE). Atomic absorption spectroscopy of the test solutions and the mass change recorded by EQCM both showed about 0.015 mg of gold leached. Since the majority of the frequency shift increase corresponding to gold oxidation occurred at -0.40 to -0.06 V during multiple cyclic voltammogram measurement, the total leaching of gold could be approximated to occur at this potential interval to give a leaching rate of ca. 6.4x10-5 mg/s-cm2.

Jan 1, 2011

By R. Mensah-Biney

The kinetics of loading of gold from bromide solution onto an anion exchange resin, PAZ-4, were investigated in a batch stirred reactor. The initial loading rate was described mathematically by a first-order reaction rate equation. The effect of agitation speed, temperature, resin particle size, resin concentration, initial concentration of gold and bromine in solution on the rate was investigated. The model described fairly accurately the loading process in terms of the variables investigated. The rate constant for the initial loading ranged from 0.5 to 1.3 x10-3 sec-1 and the half-time was 9.3 to 56 minutes. The initial rate constant increased with increasing temperature with an activation energy of 15.7 kJ/mole (3.8 kcal/mole). The rate constant was directly proportional to the concentration of the resin in solution. The subsequent reduction reaction was also modeled by the first-order rate equation and the apparent rate constant was estimated to be 3.0 x 10-6 sec-1 with a half-time of about 44 hours.

Jan 1, 1994

By R. Mensah-Biney

The kinetics of gold-bromide loading onto activated carbon has been investigated in a batch stirred reactor. The amount of gold adsorbed by the carbon was correlated with time based on a second-order equation. The rate constant for gold-bromide species onto activated carbon ranged from 0.27 to 1.2 x 10-3 (kg/t)-l(min)-l from a solution containing 25 ppm of Au, with 0.8 g carbon per liter of solution at 30° C. The equilibrium saturation capacity (Q.) was 36±3.0 kg/t from the same system. The rate of loading increased with decreasing particle size, decreasing pH, increasing temperature, and decreasing concentration of gold in solution. The calculated activation energy E. was 8.8 kcal/mole, significantly higher than those reported for physical adsorption. The equilibrium saturation capacity (Q.) increased with increasing concentration of gold in solution, but was independent of other variables such as temperature, agitation speed, particle size and pH. These rate constants and equilibrium saturation capacity for the gold-bromide species are higher than those reported for the gold-cyanide systems.

Jan 1, 1996

By P. C. Kapur

The kinetics of green pelletization in a laboratory balling drum have been studied, using pulverized limestone as a model system. The growth characteristics of green pellets were found to be extremely sensitive to the moisture content of the material. Empirical kinetic equations, which incorporate a function of specific surface of the pellets as the criterion for growth potential, have been found to describe growth in a nucleation region and in a ball growth region. The rate constants in the kinetic equations are strongly dependent on the moisture content of the material being pelletized. Size distributions of the halls at different stages of pelletizing are also discussed.

Jan 1, 1965

By A. Rodriguez-Prado, P. Kuschk, R. L. Legge, W. C. Lennox

Using constructed wetlands to chemically reduce hexavalent chromium Cr(VI) to Cr(III) from industrial and mining wastewater has proven to be feasible and efficient. Applying first-order kinetics to describe the process is simple, but in some cases a more accurate model is required to reflect the process. This paper studies the feasibility of using non–first-order kinetics to describe the reduction process. Results indicate that half- and second-order kinetics adequately described Cr(VI) reduction in laboratory wetland mesocosms. The organic carbon content played a relevant role, whether it was built up by plant growth or spiked into the feed water.

Jan 1, 2014

By B. Friedrich, N. Anastasijevic, S. Stopic

The extraction of nickel from Serbian and Western Australian lateritic ore by sulphuric pressure acid leaching (PAL) has been studied. The following parameters were tested: stirring rate, acid to ore ratio, reaction time, pressure and temperature. These studies were performed with ore samples from the Rudjinci, Serbia and Silcrete, Australia, both belonging to the laterite-silicate group of deposits. An increase of the reaction temperature and the stirring speed at a fixed acid/ore ratio showed a positive influence on nickel extraction. The decrease of the oxidation potential with time correlated with the increase in Fe(II) in solution and nickel extraction as the reaction went to completion for both ores. The target values of 95 % Ni extraction and 60 % Co extraction were attained in 5 min at 250°C for the Serbian silicate ore, at an agitation rate of 1500 rpm, 10 % solids, and acid/ore ratio of 0.40. Under similar conditions only 60 % Ni, but 69 % Co could be extracted from the Australian Silcrcte ore due to different mineralogy. The nickel extraction was shown follow a diffusion-controlled reaction model.

Jan 1, 2004

By A. E. Sobolev

The kinetics of hydrochemical oxidation of antimonite in solutions of nitric acid was studied using the rotating disk method and the factor experiment design. The dependences of the antimonite?s oxidation rate on concentration of nitric acid solutions, temperature, disk rotation frequency, and duration of interaction were determined. The adequate kinetic models allowing calculating the specific oxidation rate at any combination of the values of the influencing factors were obtained. The oxidation process is found to proceed in a mixed mode, close to chemically controlled. Gradually, as the sediments of elemental sulphur and Sb2O5 accumulate on the disk surface, the process becomes controlled by internal diffusion. The observed high (more than second) order of the oxidation rate with respect to the concentration of nitric acid was explained by the autocatalytic action of the acid reduction products. The apparent activation energy depends on the stage of interaction. At the initial stage (in a mixed mode of the process proceeding), it depends on nitric acid concentration and varies from 31.5 kJ?mol?1 (in 2 M HNO3) to 36.1 kJ?mol?1 (in 10 M HNO3). This trend indicates the weakening of diffusion limitations with a nitric acid concentration increase. When the process is controlled by internal diffusion, the apparent activation energy was found to be 14.5 kJ?mol?1. The obtained kinetic characteristics enlarge the database on hydrochemical oxidation kinetics of sulphides and can be used for the elaboration of the recommendations for the effective comprehensive exploitation of antimony-bearing ores and concentrates.

Jan 1, 2014

By N. Bazzanella

The hydrogen desorption kinetics of pure and Nb-doped magnesium hydride film samples was investigated by using a Sievert-type apparatus. The overall activation energy and the reaction order controlling desorption are (141±5) kJ mol-1H and n 4 for Mg hydride and (51±5) kJ mol-1H and n 1 for Nb-doped (5% at) Mg hydride indicating that, in the doped sample, hydrogen desorption is controlled by the H migration in transformed h-Mg layers. Structural analysis performed by X-Ray Diffraction (XRD) and Extended X-Ray Absorption Fine Structure spectroscopy (EXAFS) show that the catalytic effect of the Nb dopant is connected with the formation of NbH0.89 nanoclusters dispersed in the Mg hydride matrix. It is suggested that the catalysis process is also connected to the presence of Mg-Nb hydride interfaces where the transfer of H atoms preferentially occurs by connecting h-Mg grains and by the role of the MgH2-NbH0.89 interface as preferential site for the dissociation of the hydride phase.

Jan 1, 2006

By Wright G. A

The objective of refining in steelmaking is to reduce the concentration of impurity atoms, e.g. sulphur, phosphorus, from an initially high level to a specified low concentration. A two-film theory of refining is presented in which the rate of

Jan 1, 1980

By W. A. Hockings, G. W. Lower, K. A. Smith

The kinetics of dissolution of metallic copper in aqueous cupric ammonium carbonate solutions were investigated. The major variables studied were temperature, agitation, and the cupric, cuprous, ammonia and carbonate concentrations. The rates of copper dissolution from rotating discs were determined by measuring the weight loss. The dissolution rate increased with the square root of the disc rpm and doubled when the temperature was increased from 20°c to 40°C.

Jan 1, 1973

By Anat Deepatana

Bioleaching of nickel laterite ores is the extraction technology based on the use of heterotrophic micro-organisms and their organic acid products to dissolve metals from oxide minerals. This study examined the chemical leaching kinetics of limonite and nontronite ores with metabolites including citric, lactic and malic acids. The leaching process was found to follow the chemically controlled model. The leaching kinetics was found to be significantly influenced by the acid strength or dissociation of acids in solution. Although increasing the acid strength increased the rates of leaching, this trend was not indefinite. An optimal acid concentration that defined the fastest leaching rates was identified for each acid. The amenabilities of the minerals hosting the nickel and cobalt in limonite and nontronite to organic acid leaching were also established.

Jan 1, 2006

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

KNOWING the endpoint, or the equilibrium state, in steelmaking reactions is only part of the story. The rate at which the reactions proceed can be equally important. But the power of thermodynamics, which enables us to estimate the endpoint, is that a knowledge of the mechanism is not required. The methods of kinetics, however, are step-by-step analysis in which a knowledge of the detailed reaction mechanism is essential. As is evident from Chapter 16, a great deal of thermo- dynamic data for steelmaking are available and the underlying theory rests on a completely sound basis. This is far from the case with kinetic data and even kinetic theory. Nevertheless, it is worthwhile to examine the present state of knowledge, to see how far it may be applied to electric furnace reactions. KINETIC THEORY Heterogeneous Reactions. Classical kinetic theory and experimentation have been mainly concerned with homogeneous reactions taking place between different chemical species in a gas or liquid phase. The species are mixed together and the progress of the reaction can then be observed. This is possible because most experiments have been done at relatively low temperatures where the characteristic time for the mixing process is much shorter than the time for the chemical reaction to be completed. For example, in the homogeneous gas reaction, H2 (g) + I2 (g) 2HI (g) hydrogen and iodine may be added to opposite ends of a tube containing a diaphragm. When this is withdrawn, gaseous diffusion (and convection) mixes the two types of molecule almost completely before any hydrogen iodide molecules begin to appear. Such an experiment is inconceivable at more elevated temperatures, since the rate of the chemical process is so sensitive to temperature that reaction would be completed almost instantaneously wherever hydrogen and iodine came into contact; the rate of the mixing process would then determine the rate at which hydrogen iodide was formed. We should not, therefore, expect to observe many homogeneous reac-

Jan 1, 1964

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