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By C. J. Pretorius

More than 30 percent of the global demand for zircon (ZrSi04) is supplied by South Africa. A significant amount of the zircon is exported, and beneficiated products are then imported for industrial applications locally. Beneficiating the zircon locally could have a positive impact on the local market, since zircon is only one of many such cases. Ammonium acid fluoride serves as an alternative anhydrous fluorinating agent for zircon in the synthesis of several metal fluorides1,2. It provides an effective dry fluorinating method and is easier to handle than hydrogen fluoride or fluorine gas. Zircon exposed to extreme plasma temperatures dissociates and becomes more reactive. The reaction of the plasma-dissociated zircon (Zr02.SiO2) with the ammonium acid fluoride (NH4F.XHF, where x= 1 to 5) forms two main intermediate compounds (NH4)3ZrFr(s) and (NH4) 2SiF6(s), the latter decomposing to form volatile products at relatively low temperatures, providing easy separation of the silicon and zirconium compounds. The ammonium zirconate compound decomposes to form zirconium tetrafluoride (ZrF4), which can be further manufactured into zirconium metal, to name but one product. Data on the kinetics of the reaction of ammonium acid fluoride with zircon and plasma-dissociated zircon, combined with the thermo¬dynamic parameters of the reaction, is essential for the development of an industrial process for the production of a precursor for the manufacturing of zirconium metal, namely anhydrous ZrF4. Both the reaction kinetics and reaction parameters will be included in this study, as well as some proof that the reaction proceeds to ZrF4 on a small batch scale. If the exact reaction parameters can be pinned down, a wide spectrum of anhydrous metal fluorides can be synthesized through this fluorination route.

Jan 1, 2012

By Xiang Ma, Halvor Dalaker, Kai Tang, Stefan Andersson

Silicon carbide (SiC) is one of the most important non-oxide ceramic materials for many industrial applications and is mainly synthesized by carbothermic reduction of silicon oxide by coke above 2200°C. Replacing natural gas (mostly methane, CH4) for coke in SiC synthesis could considerably reduce energy consumption and CO2-emissions owing to higher carbon activity of CH4 at lower temperature. The generally accepted reaction mechanism is that SiC is synthesized through gaseous intermediate silicon monoxide, SiO. In the present study, the reaction mechanism for the SiO and CH4 gaseous mixture has been examined using atomic scale modelling. Molecular dynamics (MD) using a reactive force field (ReaxFF) has been utilized to examine the initial stages of reactions involving a gas mixture of SiO and CH4 and surfaces of SiC. The MD results revealed some interesting SiC formation mechanisms. The reaction energies of the critical intermediate species were also estimated by density functional theory (DFT) calculations and the implications for the force field parameters used in ReaxFF was discussed.

Jan 1, 2015

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 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 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 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

By J. Diao

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

Jan 1, 1992

By A Holmgren, W Forsling

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

Jan 1, 2005

By M. J. Adam

The U.S. Bureau of Mines is investigating the partitioning of selected complex minerals into simple phases using sulfidation reactions. Successful partitioning of complex mineralogy to simple phases may afford an opportunity to improve selective extraction of mineral constituents of economic value. The research has shown that complex minerals, such as chalcopyrite (CuFeS2) and pentlandite [(Fe,Ni)9Se]&apos; may be partitioned to the simpler phases covellite (CuS) plus pyrite (FeS2) and vaesite (NiS2) plus pyrite (FeS2), respectively. Demonstrations of these reactions were verified through long-react ion-time (24 h or more) experiments, but basic rate investigations and modeling were not included in the previous research. This report describes research aimed at determining the rate at which the complex mineral CuFeS2 converts to the simple sulfides CuS plus FeS2. Small samples of CuFeS2 were blended with elemental S prior to thermal treating under an He atmosphere for time periods up to 4 h. Products from each treatment period were characterized using metallography, chemical analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Results of the investigation revealed a rapid conversion of CuFeS2 to CuS plus FeS2 early in thermal treatment periods. As the reaction occurred, a CuS rimming of particles was observed which separated the reacting species (CuFeS2 and S) and caused a considerable decrease in transformation rate.

Jan 1, 1991

By Milorad Cirkovic

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

Jan 1, 1999

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

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

Aug 1, 1995