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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.

By M. Sinirkaya

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

Jan 1, 2010

By Milton E. Wadsworth, Ximeng Zhu

Impurity metals can markedly influence the anodic dissolution of gold in the presence of cyanide. Several important findings related to the influence of lead are reviewed and some new observations presented. Based on the effect of pH, the scan direction, and voltage, it may be shown there are three separate voltage regimes where lead influences the anodic dissolution of gold. These are related to Pb°/ HPbO2, Au-Pb /HPbO2, and HPbO2/PbC2; oxidation-reduction reactions which provide low resistance paths for electron exchange. The gold dissolution rate was determined by direct solution analysis and is compared to the rate implied by electrochemical measurements.

Jan 1, 2005

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

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

Jan 1, 2016

By Lin Li, Ahmad Ghahremaninezhad

"In this paper, the electrochemical behavior of ferric and ferrous couple on the pyrite surface was studied by application of the chronoamperometry technique in an acidic solution at room temperatures and atmospheric pressure. The effects of the pyrite origin, ferric and ferrous ions concentration on the electron transfer kinetics of Fe3+/Fe2+ reaction were probed. Tafel behavior of all the test conditions were developed. The results showed that the ferric-ferrous reaction on pyrite electrodes with different origins have a common mechanism, despite different reaction kinetics. The exchange current densities of the redox reaction have the same magnitude of about 10-5 A·cm-2, which is far lower than the value reported for the gold and platinum electrodes, but larger than that of the chalcopyrite electrode. The cathodic transfer coefficients are between 0.4 and 0.5, while the anodic transfer coefficients appear unusual with the lowest value being 0.23. It was also demonstrated that an increase of one order of magnitude of iron concentration has no clear effect on the exchange current density and cathodic transfer coefficients of Fe3+/Fe2+ redox reaction.INTRODUCTIONPyrite, FeS2, is mostly considered as a gangue mineral which frequently coexists with valuable minerals and metals, such as gold, copper and nickel. Its separation from valuable minerals can be a costly process (Chandra & Gerson, 2010). In refractory gold ores, the fine gold particles are locked inside the pyrite structure. Oxidative leaching of pyrite is a hydrometallurgical method to destroy the structure of pyrite and expose the fine gold particles to the cyanide solution in the downstream cyanidation circuit. Pyrite oxidative leaching can be achieved by oxidation of pyrite via oxygen and ferric ion(McKibben & Barnes, 1986). In fact, pyrite oxidation by oxygen and ferric is a significant source of acid mine drainage(AMD), which adversely causes serious environmental problems(V. P. Evangelou, 1995).The pyrite oxidation mechanism is accomplished in three consecutive steps: (i) pyrite is oxidized by oxygen and ferrous ion formation (Eq. 1); (ii) ferrous oxidation by oxygen and ferric ion formation (Eq. 2); (iii) pyrite oxidation by means of ferric ions (Eq. 3). Hence, both oxygen and ferric participate in the pyrite oxidation process (Moses & Herman, 1991):"

Jan 1, 2016

By Rashmi Kumar, Amit Chatterjee, Sanjay Chandra

The practice of adding alloying materials to a molten bath is an integral feature of many pyrometallurgical operations. However, very little is known about the dissolution rate and solution mechanisms of solid additives in liquid melts. In foundries where large tonnages of liquid metals are handled, there is considerable interest in achieving optimum metal quality at minimum cost. This objective is influenced by several factors and the solution is often plant specific. Though the amount, sequence and mode of ferroalloy addition vary from plant to plant, various fundamental factors determine how quickly these additions dissolve in the bath. At the Ingot Mould Foundry (IMF) in TATA STEEL blast furnace hot metal is used to cast ingot moulds. The composition of hot metal desired for making ingot moulds demands addition of 20 kg each of Ferromanganese and Ferrosilicon in the 12 T transfer ladles into which the blast furnace metal is poured at the IMF. Owing to low temperature of hot metal at the IMF, casting commences immediately and complete dissolution of the ferroalloys is often not possible. To study this aspect in detail and to evolve suitable corrective measures, a mathematical model for the melting of a solid particle in a liquid metal bath was developed at TATA STEEL. The model was validated using the data available in literature. In keeping with published work, two separate dissolution periods were identified - a "shell period" and a "free dissolution period". The maximum thickness of the crust formed around a spherical particle shortly after immersion, can be obtained by using the mathematical model which has been developed. The model can also be used to investigate the effect of various parameters such as superheat of the bath, size of the particle, etc., on the maximum crust thickness and the particle melting time. On the basis of this study, the addition of ferromanganese and ferrosilicon was optimized at the IMF in Tata Steel.

Jan 1, 1996

By Boontanjai C, Boyapati ER

Reagents used for batch flotation tests were Aeroxanthate-343 & 350, Dow Z-6, & reagent-4037 (from Benambra) as copper collectors; Na2SiO3 & Na2S2O3as gangue depressants; lime & HCl as pH regulators; and pine oil & MIBC (methyl isobutyl carbinol) as flotation frothers. A Denver Sub A flotation cell of capacity 250 gms was used for the batch flotation experiments. Atomic absorption spectrophotometer was used for copper assays and microscopy for selectivity and liberation studies. Melbourne tap water was used throughout the experiments. Unless otherwise stated, the following parameters apply to the flotation experiments: flotation impeller speed - 1300 rpm, pulp density during flotation- 22%, reagents addition - in 4 stages, total conditioning time for collectors - 8 minutes, total flotation time- 9 minutes. A variable quantity of copper mineral collector according to the test in question was added, then conditioned the pulp for 2 minutes. The froth was removed by hand, scraping the full length of the cell at constant depth every 10 seconds. No frother is required for this copper tailing flotation. Four concentrates were collected after addition of collector and conditioning at 2,4,6 and 9 minutes. The pulp volume was maintained at a constant level to yield a constant froth depth.

Jan 1, 1990

By Rodney J. Ishak

The reduction of Mn3O4 to MnO has been investigated in a thermobalance apparatus. The charge was composed of manganese ore (decomposed by heating/calcination or pre-reduction to mainly Mn304) and coke. The material was charged to a crucible, which was suspended in the balance. CO-gas was distributed through a grid in the bottom of the crucible. Two sizes of ores were used; 2.4-4.8 mm and 6.7-9.5 mm. Coke particles were in the size range 4.8-6.7 mm. Experiments were conducted in the 900-1100°C temperature range. The composition of the product gas was monitored continuously. External mass transport between bulk gas and particle surface does not seem to limit the rate of reduction. Assuming that both diffusion through product layer and chemical reaction at the interface between MnO and Mn304 are rate controlling, the data was tried both in a shrinking core model and in a grain model using regression. The grain model gives the best physical description of the process, because the reactant is in fact a porous medium. With this model the effective diffusivity was calculated to be in the 1.5-6.10-5 m2/s range. The pore size was mainly between 0.1 and 10 um.

Jan 1, 2003

By Rodney J. Ishak

The reduction of Mn3O4 to MnO has been investigated in a thermobalance apparatus, The charge was composed of manganese ore (decomposed by heating/calcination or pre-reduction to mainly Mn3O4) and coke. The material was charged to a crucible, which was suspended in the balance. CO-gas was distributed through a grid in the bottom of the crucible. Two sizes of ores were used; 2.4-4.8 mm and 6,7-9.5 mm. Coke particles were in the size range 4.8-6.7 mm. Experiments were conducted in the 900-1100°C temperature range. The composition of the product gas was monitored continuously. External mass transport between bulk gas and particle surface does not seem to limit the rate of reduction. Assuming that both diffusion through product layer and chemical reaction at the interface between MnO and Mn)04 are rate controlling, the data was tried both in a shrinking core model and in a grain model using regression. The grain model gives the best physical description of the process, because the reactant is in fact a porous medium. With this model the effective diffusivity was calculated to be in the 1.5-6.10.5 m2/s range. The pore size was mainly between 0.1 and 10 um,

Jan 1, 2003

By S. Joshi, E. Asselin

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

Jan 1, 2011