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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 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 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 George W. Lower, William A. Hockings, Donald A. Kaczynski

The rate of dissolution of polycrystalline metallic copper in aqueous cupric ammonium nitrate solutions in the non-film-forming region was investigated by the rotating disc method. The investigation was performed in solution concentration ranges applicable to hydrometallurgical processes. This investigation was an extension of a study on the cupric ammonium carbonate system previously reported by Smith, Lower and Hockings, in which the following kinetic model was proposed: (1) Diffusion of cupric ammine ions to the copper surface; (2) Forward reaction - first order reaction of cupric ammine ions with metallic copper; (3) Reverse reaction - disproportionation of cuprous ammine ions to metallic copper and cupric ammine ions ; and (4) Diffusion of cuprous ammine ions from the copper surface. The nitrate system was selected for this study because it simplified the determination of the ionic composition of the solutions. The variables studied were stirring speed and cupric, ammonia, and nitrate concentrations. The dissolution rate increased linearly with at low values of but exhibited increasingly negative deviations from linearity at higher values of m. The rate also increased with increasing cupric concentration but decreased with increasing ammonia and nitrate concentration. Good agreement was obtained between the experimental rate data and the proposed model. Further verification of the model was indicated by the close agreement of the diffusion coefficient calculated from the data and comparable literature values.

Jan 1, 1974

By J. Yao

Synthetic indium-bearing zinc ferrite (IBZF) was mechanically activated by a tumbling mill. Subsequently, the behavior and kinetics of leaching zinc and indium from the initial IBZF and activated IBZF in sulfuric acid solution were investigated. The results demonstrate that the tumbling ball milling enhances the leaching reactivity of IBZF and increases the zinc and indium extractions. The reaction temperature and H2SO4 concentration have an important effect on leaching zinc and indium from the initial IBZF and activated IBZF. The kinetic model -ln(1-x) = kt was used to describe the kinetics of leaching zinc and indium from the initial IBZF and activated IBZF and to calculate the kinetic parameters. The tumbling ball milling causes a decrease in activation energy and reaction order, which indicates that the dissolution of IBZF after mechanical activation by a tumbling mill becomes less sensitive to temperature and H2SO4 concentration. For the zinc leaching, the activation energy decreases from 73.9 to 70.3 kJ/mol and the reaction order decreases from 0.72 to 0.70. For indium leaching, the activation energy decreases from 78.1 to 73.5 kJ/mol and the reaction order decreases from 0.82 to 0.69. It is found that the dissolution rates of the initial IBZF and activated IBZF are controlled by surface chemical reactions.

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

THERE are two general types of scientific approach to a problem. One approach, which is the more widely known, involves an analysis of the situation at the beginning of the experiment; this is followed by an analysis of the situation at each instant of time during the experiment and leads to a-detailed description of the prevailing conditions at the end of the experiment. Suppose, for example, we wish to predict the final rest position on a billiard table of a ball moving initially in a certain known direction with a known speed. The obvious approach is to estimate or measure off its course by consideration of angles of rebound, taking account of the "English" or spin if necessary and finally estimating from experience (or calculating from coefficients of friction) the slowing down occasioned by friction, thus establishing the point of the course at which the ball may be expected to stop. Any interference with the calculated course occasioned by collision with an unanticipated object would obviously cause us to revise drastically our estimate of the rest position. This general method of approach characterized by detailed description of how one situation developed from another seems intuitively appealing and is the most widely known method. There is no doubt that it gives very satisfying results when it can be used. There is a second general method of approach. In this method, the final state of a system is predicted from knowledge of general broad principles and their application, considering only the restrictions imposed upon the system. It is unnecessary to follow the course in detail; intermediate steps are not even considered. For example, if the billiard table mentioned in the first paragraph were tilted to one corner, one could predict that the final resting place of the ball would be in that corner; this prediction can be made independent of any particular course the ball may follow. This second general method of attacking problems is the one used in thermodynamics. There its use is so outstand-

Jan 1, 1951

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

By Li Yuhai

Kinetics of non-isothermal precipitate process and crystal growth of perovskite (CaO ? Ti02) phase in CaO-TiOz-Si02-AlP3-MgO system were studied. The experimental results show that the relative volume fraction can be described by the equation given by K. Matusita et at. and the experiential expression of average crystal radius was obtained. The particle coarsening in non-isothermal process has important effects on the crystal growth of perovskite phase.

Jan 1, 2000

By Yasuhiro Konishi

Hydrolytic stripping is the process in which metal ions are simultaneously stripped from a loaded cation-exchange solvent extractant and precipitated as oxides or hydroxides. Hydrolytic stripping is usually effected by contacting the loaded organic phase with water at elevated temperatures. The possibility of using hydrolytic stripping to prepare ceramic powders with controlled size and morphology is now being evaluated for different systems, using carboxylic acid extractants. As part of this work, mathematical models were developed to describe the kinetics of nucleation and growth of nickel ferrite particles. This paper describes the development of the models, along with estimation of key parameters appearing in the rate equations from experimental data.

Jan 1, 1990

By E Oktay, I Yusufoglu, C Kahruman

Powder and spherical pellets of MoO2 were oxidised under controlled conditions in the temperature range 674-791 K at oxygen partial pressures of 8.1-30.4 kPa. Weight increase during the reaction was determined by thermogravimetric analysis. It was concluded that the reaction is 0.6th order with respect to oxygen concentation and that the activation energy is 148 kJ/mole. In experiments conducted with powder, fast transfer of reaction heat to the gas phase created isothermal conditions, but the temperature of pellets rose by a maximum of 54 K at 674 K and 105 K at 791 K. The rise in temperature caused structural changes such as sintering and crack formation, which had a considerable effect on the reaction rate. The findings should be taken into account in the design of equipment and choice of operating conditions for roasting MoS2

Jun 21, 1905

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 Alexander E. Sobolev

The kinetics of oxidative dissolution of lead sulfide in solutions of nitric acid and sodium hypochlorite was studied using the rotating disk method and the factor experiment design. The dependences of the PbS dissolution rate on concentration of oxidant (HNO3 or NaOCl), temperature, disk rotation frequency, and duration of interaction were determined. The adequate kinetic models allowing calculating the specific dissolution rate at any combination of values of the influencing factors were obtained. As a result of the complex analysis of kinetic parameters, the modes of the each process proceeding were established, their macromechanisms were determined, and the limiting stages of the oxidative dissolution processes were revealed. The dissolution kinetics of lead sulfide in solutions of nitric acid was found to have several regimes. At HNO3 concentrations below 0.5 mol/L, the process proceeds in a mixed mode close to a diffusion-controlled. It is caused by low oxidative activity of HNO3 and considerable diffusional diffuculties at this acid concentration range. At the nitric acid concentrations more than 0.5 mol/L and less than 6.0 mol/L, the process was found to be kinetically controlled. The limiting stage of the interaction is the surface chemical reaction. The observed relatively high order of the dissolution rate with respect to the concentration of HNO3 was explained by the autocatalytic action of the acid reduction products. At nitric acid concentrations exceeding 6 mol/L, the process proceeds in a mixed mode close to a diffusion-controlled, and the dissolution rate sharply decreased that was explained by a decrease in the solubility of reaction products. When lead sulfide is dissolved in sodium hypochlorite solutions, at first time the amount of PbS transferred into solution remains close to zero. Gradually, as time goes, this amount begins to increase sharply. The dissolution rate rises and reaches the maximum value, further remaining constant. At the steady-state regime, the dissolution rate is independent of the duration of interaction and disk rotation frequency. The process was found to be kinetically controlled. The limiting stage is likely to be chemical reaction on the surface of solid lead sulfide. The obtained kinetic characteristics enlarge the database on hydrochemical oxidation kinetics of sulfides and can be used for the elaboration of the recommendations for the effective comprehensive exploitation of lead-bearing ores and concentrates. Keywords: lead sulfide, nitric acid, sodium hypochlorite, hydrochemical oxidation, dissolution kinetics

Sep 1, 2012

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