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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

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 Taiping Lou

The coarsening process of precipitates in non-equilibrium systems was studied, and then a physical model of coarsening was proposed. The coarsening process of CaO'TiO2 in MgO-TiO2-Al2O3-SiO2-CaO-CaF system was investigated. It is shown that the coarsening process by the model predicting is agreed with the experimental results.

Jan 1, 2000

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]' 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 A. Warczok

The mechanisms and kinetics of copper oxidation and reduction have been investigated in small scale thermal gravimetric experiments as well as in laboratory pilot scale, packed bed reactors. With blister copper flowing gravitationally down through a packed bed of ceramic particles, counter-current to low oxygen containing combustion gases, the rate of oxidation was found to be very high due to the large surface area created. Similarly, reduction by flowing copper through a packed bed of charcoal lead to rapid de-oxidation. Based on these laboratory measurements, fundamental rate data have been obtained. Modeling of industrial sized packed bed reactors using the laboratory results, opened up the possibilities of developing a new, very intensive, continuous process for copper fire refining. The developed mathematical model together with a computer process simulator, allowed for the design of the industrial-pilot installation to be built and tested at the ENAMI Paipote smelter in Chile.

Jan 1, 2007

By M. I. Brittan

SYNOPSIS The key reactions of the copper segregation process have been studied with a view to establishing the kinetics of the system. The investigation was carried out using two refractory copper ores from the Zambian Copperbelt in a small-scale, fluidized bed, chloridization reactor. The rate of chloridization of the copper in the ores is compared with the rate of volatilization of the cuprous chloride produced and with the rate of reduction of the cuprous chloride to form segregated metallic copper. In conjunction with available data on the rate of production of hydrogen chloride in a segregation system and with due regard to the conditions applicable in a TORCO reactor, it is concluded that the chloridization reaction is the major rate limiting step of the process. Factors influencing the rate of this extraction step and aspects of its mechanism are examined. The findings have confirmed the validity of the existing theory of segregation and provide insight as to the viability of the system of reactions involved in the copper segregation phenomenon. Experimental results which relate to observations made in the course of TORCO plant operation and segregation studies are discussed.

By M. I. Brittan

Discussion Dr R. E. Robinson (Fellow): The author must be congratulated on a very meticulous and self-contained piece of work. It is indeed a pleasure to read a paper that is so clearly and systematically laid out, and where the conclusions and the testwork conducted have been so clearly described. The paper is complete in itself, which makes it very difficult for someone who is not intimately involved in the whole Torco project to make any comments on its content. However, two points that, strictly speaking, fall outside the scope of the paper are of considerable interest. The first relates to the particle size of the material treated. In the paper, the testwork is confined to one standard particle size (minus 60 plus 100 mesh). The essential feature of the paper is to indicate that the rate-controlling reaction in the whole segregation process is the rate of reaction of the ore particles with the reducing agent and the hydrogen chloride. One wonders, therefore, to what extent this relatively slow rate of reaction is affected by the particle size of the ore itself. One imagines that the reaction must take place by contact of the hydrogen chloride with the surface of the mineral particles, and it is reasonable to suspect that the rate of diffusion of the copper ions to the surface is a relatively slow process and is thus the limiting factor in this particular rate of reaction. It is possible, for example, that the improvement obtained, when the ore is subjected to reducing conditions before the chlorination, is due to a breakdown in the crystal structure of the original particle. This breakdown is brought about by the reduction and by the consequent increase in surface area available for reaction with hydrogen chloride. Can the author indicate whether any work has been done along these lines, and whether it has been established that the reaction depends on the surface area available? The second point relates to the application of this kinetic study to the actual operation of a Torco reactor. It was once planned to feed the sodium chloride, together with the reducing agent, into the top of the segregation chamber. In the paper, the author mentions that it has now been established that the segregation chamber behaves, to all intents and purposes, as a fluidized bed, and that there is, therefore, a rapid evolution of gas in the lower regions of the chamber, which, it is imagined, displaces the gas phase rapidly. Since the reaction between sodium chloride, water vapour, and the aluminium silicates in the ore is extremely rapid, one wonders how much of the hydrogen chloride produced is removed from the reaction zone before it has had time to react with the copper minerals. The extremely low consumption of sodium chloride (which is a vital feature of the Torco process) must depend on an extremely rapid circulation of the hydrogen chloride gas to all the ore particles in the segregation chamber. One wonders, therefore, if a system for the introduction of the sodium chloride into the bottom regions of the chamber might not result in even greater efficiency in the utilization of sodium chloride. ProC D. D. Howat (Fellow): All of us who have been concerned with the study of chemical reactions at high temperatures are keenly interested in kinetics and are well aware that this is not an easy study experimentally. Dr. Brittan is to be congratulated on the development of neat experimental methods and for his full discussion of the results obtained. Although the segregation process for the extraction of copper from oxide and silicate ores has been known for almost fifty years, the fundamental chemical and physical changes involved have been little understood and the fundamental data are very scanty. The work now in progress at A.A.R.L., together with that sponsored by the Anglo American Corporation in other research institutions throughout the world, is bound to produce new fundamental data and a much more complete understanding of this rather fascinating process. It is already apparent that some of the old and well-worn chemical reactions that were postulated to occur, just cannot take place in the way which was formerly accepted. Dr Brittan's work, carefully conducted and thoroughly analyzed as it has been, still leaves us with one great outstanding problem. The thermodynamic data and the possible reactions set out in Table I (page 281) of his paper leave us asking, in complete despair, how can copper be converted into a volatile chloride in the presence of HCl, CO and carbon at temperatures about 800°C? The thermodynamics all combine to show that copper should be reduced to metal as the first step in the process. This brings us right up against the second problem. If copper were reduced to the metal how would HCI convert it to the volatile chloride? On top of these problems is the unknown reason for the very high speed of reaction between CO, HCI and the ground copper ore. Still further into the region of the unknown is the reaction by which gaseous hydrochloric acid is produced in the actual process. Perhaps Dr Brittan is feeling grateful that he doesn't have to try to explain this reaction-at this stage of the research programme at least. The results very clearly show that both CO and HCl gas are essential for rapid production of the volatile copper chloride. Dr Brittan states that 18 minutes were required to attain 83 per cent extraction with HCl gas alone and this was reduced to 4 minutes when CO was

Jan 2, 1970

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

By G. R. Chaudhury

Many base metals, such as copper, lead and zinc, are commercially extracted by thermal processing of sulphide concentrates. However, owing to the depletion of high grade sulphide ore reserves and to environmental legislation, efforts have been in progress for some years to develop methods for the extraction of metals from lower-grade oxide ores and secondary resources, and there are now examples of commercial-scale operations.

Dec 1, 1995

By X Dai

This paper investigated the loss of cyanide via oxidation in CIP or CIL processes by relating the cyanide oxidation to its major oxidation product, cyanate. The results showed that the oxidation of both free cyanide and copper cyanide complexes are substantially enhanced by the presence of carbon. The rate of cyanide oxidation was found to occur in the order: Cu(CN)32- > CN- > Cu(CN)2-. The cyanide oxidation rate in the presence of copper and carbon increased significantly with increasing dissolved oxygen concentration, typical of CIL vs. CIP conditions. Cyanide oxidation rate of iron, zinc or nickel cyanide complexes was minimal.

Jan 1, 2011

By N. Kanari

The kinetics of oxychlorination of MgO by Cl2+O2 was studied in the temperature range of 850 °C - 1025 °C, using thermogravimetric analysis. The effects of C12/02 ratio, gas velocity, temperature and partial pressure of reactive gases on the reaction rate were investigated. The oxychlorination process was characterized by an apparent activation energy of about 214 kJ/mol. The reaction orders with respect to C12+O2. C12 and O2 at 950 °C were about 0.65.0.98, and -0.37, respectively. Some data about oxychlorination kinetics of MgO, Cr2O3, and MgCr2O4 contained in chromite were compared. Efficiency of using oxychlorination for the removal of iron oxides contained in magnesia was demonstrated.

Jan 1, 1999

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.