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By Michael Nicol

A quantitative description of hydrometallurgical operations depends primarily on an understanding of the kinetics of the chemical and physical processes that take place in such operations. This paper will review the current status of kinetics in hydrometallurgy in terms primarily of the author’s experience in diverse unit operations. A distinction will be made between the popular use of models based on limited kinetic data and mechanisms which reflect the actual elementary chemical or physical steps involved in an overall process. Several examples will be used to illustrate this distinction. The proliferation of published papers of declining quality has resulted in the bequest to later researchers of outdated and often incorrect conclusions by a process that is often difficult to reverse. Some examples of these mysterious concepts will be examined and hopefully reversed. Finally, several examples will be given that identify significant gaps in our understanding of the kinetics of important processes that remain unresolved.

Jan 1, 2014

By C. Hecker, J. A. Garcia

To determine the kinetic reaction mechanism, electrochemical experimental techniques of stationary polarization, linear voltammetry and faradaic impedance were used. Gold electrodeposition experiments were realized using an electrolysis cell, provided· by a rotary disk of vitreous carbon and or' platinum counter electrode of platinum mesh and reference electrode. Using an automatic measurement system voltarnmograrns and Nyquist faradaic impedance spectra were obtained. In this paper, responses for different cases were analyzed through faradaic impedance criteria, considering several kinds of diagrams obtained. The importance diffusion influence of aurocyanide ions and adsorption as controlling steps previous charge transfer was verified. A model of proposed mechanism is discussed.

Jan 1, 1997

By C. E. Jordan

Direct digestion of phosphate ores by the acid-alcohol method offers improved leaching selectivity for the exclusion of iron and aluminum in the product acid. The leaching kinetics of this process will have a major role in the eventual application of this technology. The Bureau of Mines investigated apatite dissolution to determine the reaction rate and mechanisms of the leaching kinetics. The dissolution kinetics were monitored on various sized fractions of pure apatite. The "shrinking-core" kinetics model was applied to the data to determine the rate controlling mechanisms. For each size fraction, the initial reaction rate was controlled by the dissolution reaction. After an hour the dissolution rate slowed indicating a diffusion controlled reaction caused by the formation of calcium sulfate hemi-hydrate coating on each particle. For complete dissolution of the apatite, the phosphate rock should be ground to near 10 µ m size.

Jan 1, 1993

By Baozhong Zhao

Experimental results have shown that fluxing with soda ash (Na:zC03) can remove As and Sb from molten copper at the rate of As>Sb, but is relatively ineffective in removing Hi. The rate of impurity removal is controlled by impurity mass transfer in the metal phase. In this paper, a mathematical model was developed to describe the impurity removal phenomena. The model incorporates the effects of molten bath mixing intensity, soda ash feeding rate, oxygen content in the molten copper and soda ash fluxing by surface addition and injection. The model predictions are in good agreement with experimental results and may be used in designing large scale tests.

Jan 1, 1996

By S. D. F. Rocha, A. L. A. SANTOS, E. M. A. BECHELENI, R. M. Papini, P. R. M. Viana, F. P. C. Silvas

The kinetics of atmospheric sulfuric acid leaching from a Brazilian nickel laterite ore was assessed using distinct reducing agents and ore mineralogy. This transitional ore contains 1.63% Ni distributed as 1.27% in coarse size (− 500 + 150 μm), mainly as silicates (lizardite and chlorite—28.6%), and 2.06%in the fines fraction (− 75 μm), mainly as iron oxy-hydroxides (goethite and hematite—49%). The effects of temperature, acid concentration, reducing reagent type, and concentration were evaluated. The − 75 μm fraction limited the leaching efficiency and the use of reducing media with thiosulfate improved leaching and Ni-Fe selectivity. However, at constant Eh of 626–743 mV and a pH range between 0.2 and 1.1, no substantial rise in metals extraction, except for Co and Mn, has been observed. In order to determine the process control at 95 °C, two regions in the extraction curves were used in combination with the shrinking core model. Control by porous diffusion was observed and the kinetic constant was found to be in the order kFe<kNi<kMn<kCo<kMg for atmospheric leaching without Eh control. In reducing media for the first 15 min of leaching, the kinetic constant was found to be kFe<kNi<kMg≅kCo<kMn as derived from Ni disseminated into iron oxides structures.

Oct 7, 2020

By S. D. F. Rocha, A. L. A. SANTOS, E. M. A. BECHELENI, F. P. C. Silvas

Hydrometallurgical processes are needed to extract nickel (Ni) when it is disseminated in mineral matrix. High-pressure acid leaching (HPAL) and atmospheric acid leaching (AAL) are alternatives, and AAL has the advantage of requiring mild temperatures and pressure. Reducing-reagent tests improved the extraction of metals for the specific limiting portion of the ore. Low dosage of sodium thiosulfate presented better selectivity and safer operating conditions, allowing metal extractions of 50–62 percent at 95 °C. However, the low extraction rate obtained for Ni and the similar levels of impurities — magnesium (Mg), manganese (Mn), cobalt (Co) and iron (Fe) — extracted may represent economical and technological challenges in the downstream process.

By E. V. Konopleva, H. J. McQueen

"The isothermal bainite transformation kinetics of low- and medium-carbon alloy steels after hot deformation and the rmocycling treatment (TC) has been studied by the magneto - metric method. Deformation was produced by rolling at 800°C-1000°C. TC included three cycles of rapid (30°C/s) electro-heating up to 900°C-1000°C followed by quenching.Hot deformation retards bainite transformation in the lower part of bainite range (<400°C) and accelerates it in the upper part (>400°C). The effect is greater for higher strain and lower deformation temperature. Deformation also diminishes the overall bainite fraction below 400°C and increases the completeness of reaction above 400°C.Thermocycling provides more uniform ultrafine austenite grains with average size of 3 µm -4 µm compared to 12 µm -14 µm after conventional heating. The transformation rate after TC was almost the same as after conventional heating in low-carbon steel but was faster in medium-carbon with no change in the completeness of reaction. The degree of acceleration increased with rise of transformation temperature.There are a number of factors which are responsible for a change in bainite transformation kinetics in austenite deformed at high temperatures or subjected to TC. One of the most important factors is the refinement of structure, another one is structural and chemical inhomogenity of austenite due to deformation or to rapid heating. To estimate the contribution of these factors, ?-transformation was studied after different austenitizing conditions (low-temperature heating at 850°C- 950°C; high-temperature heating at 1100°C; step treatment – austenitizing at 1100°C, then cooling to 950°C-850°C). The results obtained make it possible to conclude that the structural and chemical inhomogeneity of austenite activate the bainite reaction while the grain refinement retards it. Intensity of the effect produced by each factor depends strongly on the steel composition."

Jan 1, 1997

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 K. H. Lee

The rate of beryllium dissolution from a low-grade ore was studied in sulfuric acid solutions. The effect of stirring speed, sulfuric acid concentration, particle size and temperature on the rate of dissolution of beryllium was established. The results of the study showed that the dissolution rate is independent of stirring speed within the range of 250-1000 rpm but depends on 1/2 power of the sulfuric acid concentration. The dissolution rate increases exponentially with decrease in particle size and the maximum attainable rate of extraction with respect to particle size is 6.6 x 10 mol dm min. The apparent activation energy (^E) for the dissolution reaction is 54.4 kJ/mol (13.0 kcal/mol). Based on this magnitude of the activation energy, it is concluded that a surface chemical reaction is the rate limiting step for the temperature range (70° -100°C) investigated.

Jan 1, 1988

By Paul L. Wichlacz

A mathematical model of growth and ferrous iron oxidation for attached bacteria was applied to rotating biological contactor (RBC) units treating acidic mine drainage. The model describes attached bacterial growth as a saturation function, where the rate of substrate utilization is determined by a maximum substrate oxidation rate constant, a half saturation constant, and the concentration of substrate within the RBC. The maximum oxidation rate constant was proportional to flow rate and the substrate concentration in the reactor varied with influent substrate concentration. The model was tested at three separate sites and with three different size RBC units. The ability of the model to predict the rate of iron oxidation under all test conditions was significant. The accuracy of the model was found to be affected by unit size and vary with specific test site.

Jan 1, 1985

By J. A. Brierley, C. L. Brierley, K. A. Prisbrey, R. W. Bartlett, J. G. Harrington

Bacterial oxidation of gold-encapsulating sulfide minerals in low-grade refractory ores was investigated over a period of one year. Crushed ore samples were held in wet, bacteria-inoculated, aerated columns. Sulfide mineral oxidation data were correlated with subsequent gold cyanide extractabilities. Experimental results for both sulfide conversion and gold extraction were compared with a biooxidation kinetics model that incorporates rock size, mineral grain size, and heterogeneous pyrite reaction kinetics. Using the model, extrapolations were made over three years for biooxidation of ore in large stockpiles. Ferric ion (oxidant) diffusion in the solution-filled pores of the rock matrix does not control the biooxidation kinetics of ore crushed to -25 mm.

Jan 1, 1993

Kinetics of bubble-particle interaction, surface hydrophobicity and interfacial phenomena in sulfide mineral flotation are discussed in this paper. Results of the measurements of a bubble and mineral induction time (IT) and detachment force (DF), vacuum of bubble evolution (VE) and mineral floatability are discussed for pyrite, galena, chalcocite and chalcopyrite. Natural wetting and wetting induced by xanthates with different lengths of alkyl chains are examined. Experiments show the existence of several maxima of hydrophobicity on dependences of pH and electrochemical potential. These maxima are attributed as the reflection of mineral surface heterogeneity due to xanthate adsorption and the presence of cationic and anionic centres with uncompensated positive and negative charges. These charges can be neutralised by both regulation pH and applied potential. The aim of this paper is to evaluate a thickness of the rupturing film and to estimate how long the bubble-mineral interactions are according to the experimental values of IT, in order to develop a procedure for comparing of the results of DF and atomic force measurements in the same dimensionality, and to compare the results of the experimental studies on the wettability of sulfides with those predicted by the models of physics of capillarity.

Jan 1, 2005

By J. L. Hendrix, R. B. Dix

A study was made of the United States Bureau of Mines chlorine-oxygen leaching process for complex sulfide concentrates. The investigation sought to determine the kinetic order and mechanisms involved in the reactions between galena and sphalerite with chlorine. The influence of copper on the extraction rates was also studied. It has been shown that the rates of reaction of chlorine in aqueous solutions with sphalerite and galena are both zero order at 373 K with rate limiting step being the chemical reaction. Addition of cupric chloride increased the extractions of both lead and zinc.

Jan 1, 1981

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 Jagannath Pal, Ammasi Ayyandurai

Hematite ore pellets require a much higher induration temperature than magnetite ore pellets because no exothermic heat is generated due to oxidation inside during induration-like magnetite pellets. Carbon is used as in situ heat source in hematite ore pellets which can reduce temperature requirement in the induration strand and hence decreases energy consumption. Many investigators have reported that a 0.8–1.25% addition of carbon in hematite pellets can improve the pellet properties also. However, to investigate the exact role of carbon in hematite pellets, its reaction mechanisms and kinetics study are required which have not been done so far. Therefore, the reaction mechanism and its kinetics have been studied in this investigation. It has been found that carbon reaction happens in pellets from the surface towards the center in a topochemical manner which is controlled by pore diffusion of gas, and its activation energy is around 52 k J mol− 1. It is also found that apart from in situ heat, carbon in hematite pellets enhances diffusion bonding which improves pellet properties. This study ascertains the exact role of carbon in hematite pellets which may help operators to use carbon effectively to reduce energy consumption and improve pellet properties.

Nov 6, 2022

By I. Iwasaki, K. A. Smith, X. Cheng

A cathodic decomposition model was examined for both pyrrhotite and chalcopyrite in an attempt to analyze the formation of surface coatings in deoxygenated solutions at natural, near neutral pH. Combination potentials established between the mineral-grinding media pair were simulated by applying a potential of -0.455 V (vs. a standard hydrogen electrode) either to a pyrrhotite or to a chalcopyrite electrode. Chronoamperometry was used to study the polarization behaviors and alteration of mineral surfaces through cathodic processes. The kinetic parameters of cathodic decomposition of pyrrhotite and chalcopyrite were determined and compared. It was concluded that pyrrhotite decomposed faster than chalcopyrite in near-neutral pH solutions. Both minerals were then covered by a film consist¬ing mainly of iron hydroxides, which adversely affected their flotation.

Jan 1, 1999

By Isabel F. Barton, J. Brent Hiskey

Chalcopyrite (CuFeS2) is the earth’s most abundant copper ore mineral, but is refractory to leaching with sulfates, chlorides, and other common lixiviants and oxidants. This has led to increasing research into alternative lixiviants for recovering Cu from chalcopyrite. Here, we review the leach kinetics of chalcopyrite in glycine, ionic liquids, and methanesulfonic acid, compared to baseline ferric sulfate and ferric chloride. Glycine (CH2NH2COOH) has long been used in applications such as biocatalysis and electroplating, and has recently been examined as a lixiviant for whole ores and concentrates of both copper and gold. It is nontoxic, biodegradable, and capable of strongly complexing Cu2+. Compatible oxidants are peroxide, dissolved oxygen, and ferric sulfate. Chalcopyrite leaching rate in glycine is chemical reaction-controlled, but the effects of grain size and the reaction orders with respect to lixiviant and oxidant concentrations and mass transfer vary. The use of ionic liquids as a leaching agent for chalcopyrite has been extensively investigated in recent years. This system is based primarily on the use of the imidazolium molecule (C3H5N2), which is a planar 5-member ring structure. This lixiviant has been applied to the leaching of chalcopyrite in the form of pure mineral, concentrates, and ores. Kinetics of ionic liquid leaching of chalcopyrite vary substantially depending on the type and concentration of ionic liquid. Methanesulfonic acid (HCH3SO3) is one of the newest lixiviants available in leaching, having only been examined in the last decade. It has been examined as a substitute for sulfuric acid, since it is less corrosive, is biodegradable, and breaks down to carbon dioxide and sulfate over time. The rate of copper leaching from chalcopyrite by methanesulfonic acid is controlled by diffusion and exhibits a strong dependence on oxidant type and concentration. Despite promising reaction rates and total extraction by some of these novel lixiviants, comparison with baseline ferric sulfate and ferric chloride systems makes it doubtful that any will be commercially viable in the near term. Only at very high reagent concentrations and temperatures, and/or very fine grain size, did any of the systems perform comparably to the much cheaper ferric chloride at extracting Cu from chalcopyrite. Most had similar overall reaction rates and total extraction to ferric sulfate, which is relatively common and cheap. However, the leaching kinetics of these novel lixiviants offer valuable insight into the dissolution behavior of chalcopyrite in various systems.

Jan 1, 2019

By E. A. Brocchi, D. H. Gameiro, P. K. Jena

Carbon tetrachloride was found to be a very efficient chlorinating agent for anatase concentrate, even at the low temperatures that were investigated (250-400 degrees C). For example, at 400 degrees C about 90% of the anatase concentrate was found to have been chlorinated within 60 minutes

Jun 13, 1905

By J. D. Steenkamp

In a paper presented at the Heavy Minerals Conference 2001 a laboratory scale investigation on the beneficiation of an ilmenite containing waste stream by magnetizing roasting was reported1.This waste stream contained a high concentration of ilmenite, which was contaminated by chromite and other gangue minerals. Interpretation of the results of the investigation was based on the assumption that during magnetizing roasting of an ilmenite concentrate, under the oxidizing conditions, the magnetic properties of the chromite would remain constant. In this article thefollowing hypothesis was tested: The magnetic susceptibility of chromite would remain constant during magnetizing roasting of an ilmenite concentrate under the oxidizing conditions reported by Gouws and Van Dyk1. The results of this study indicated that the hypothesis is not true. The increase in the magnetic susceptibility is not significant though and it is expected that it will not influence the final ilmenite quality to a large extent. Based on the assumptions that the bulk magnetic susceptibility of the waste stream samples represents that of the ilmenite in the waste stream, and the bulk magnetic susceptibility of UG1 chromite that of the of chromite in the waste stream, the results also served to confirm that the waste stream with a high chromite content should be roasted under oxidizing conditions, in a reactor with a well-defined retention time distribution (i.e. a fluidized bed reactor), at a roasting temperature of 750°C (rather than the higher temperature ranges of 800°C and 850°C).

Jan 1, 2003

By J. D. Steenkamp

In a paper presented at the Heavy Minerals Conference 2001 a laboratory scale investigation on the beneficiation of an ilmenite containing waste stream by magnetizing roasting was reported1.This waste stream contained a high concentration of ilmenite, which was contaminated by chromite and other gangue minerals. Interpretation of the results of the investigation was based on the assumption that during magnetizing roasting of an ilmenite concentrate, under the oxidizing conditions, the magnetic properties of the chromite would remain constant. In this article the following hypothesis was tested: The magnetic susceptibility of chromite would remain constant during magnetizing roasting of an ilmenite concentrate under the oxidizing conditions reported by Gouws and Van Dyk1. The results of this study indicated that the hypothesis is not true. The increase in the magnetic susceptibility is not significant though and it is expected that it will not influence the final ilmenite quality to a large extent. Based on the assumptions that the bulk magnetic susceptibility of the waste stream samples represents that of the ilmenite in the waste stream, and the bulk magnetic susceptibility of UG1 chromite that of the chromite in the waste stream, the results also served to confirm that the waste stream with a high chromite content should be roasted under oxidizing conditions, in a reactor with a well-defined retention time distribution (i.e. a fluidized bed reactor), at a roasting temperature of 750°C (rather than the higher temperature ranges of 800°C and 850°C).

Jan 1, 2003