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By V. A. Luganav

The behavior of arsenopyrite under heating has been studied by many scientists. It has been already established that under heating at more than 650°c and without air access the arsenopyrite dissociates with the formation of one atom arsenic. Under vacuum the dissociation process begins at 5500C with the formation of elemental arsenic. The residue of dissociation process contains pyrrhotite and throilite. In the presence of pyrite, arsenopyrite dissociates under lower temperature and with a higher velocity than without it. The industrial realization of fool scale processing of arsenic bearing raw materials is possible only by the use of standard equipment and oxygen containing blast. In this view the paper presents the results of the study on the effect of oxygen in the gaseous phase and its addition into the charge of pyrite in the process of arsenopyrite decomposition. Thermodynamic analyses showed that under thermal processing of arsenopyrite in the presence of pyrite and limited quantities of oxygen in the gaseous phase the formation of arsenic sulfides is possible according to the following reactions:

Jan 1, 2003

By Daniel K. Kim

The charge for the copper refinery is a mixture of anodes produced at San Manuel from BHP source concentrate and copper purchased from external sources. Control of unwanted impurities in the tankhouse - is very important and beneficial. Currently available removal/recovery technologies were reviewed for the control of bismuth and antimony levels in the electrolyte. Recent studies have focused on solvent extraction (SX) technology and generated successful results for the removal and subsequent recovery of bismuth and antimony. The SX system employs the reagent, ACORGA SBX-50, in conjunction with a patented high chloride stripping system. The latter enables recycle of the eluant, avoiding the high costs associated with conventional systems, such as regeneration of resin. Concerns over potential transfer of organics and chloride ion to the electrolyte were readily addressed, solved and demonstrated using conventional, established technology. This paper describes the benefits of electrolyte purification, the flexibility afforded by the SX system, the operational practices necessary for maintaining adequate control of bismuth and antimony impurities in the electrorefining environment and possibilities for future development /exploitation of the Zeneca SX system at the San Manuel refinery.

Jan 1, 1998

By Mahesh C. Meyer Jha

AMAX has developed a chloride refining process to produce pure nickel and cobalt metals from mixed sulfide .precipitates, Metal chloride solutions, generated in a hydrochloric acid leaching step and purified in a solvent extraction circuit, are converted to metal oxides .and HCI gas by pyrohydrolysis. A pilot plant consisting of a 30-inch diameter fluidized bed reactor and other ancillary units was designed, constructed, and operated for over one year. Process design was aimed at minimizing energy consumption, maximizing conversion efficiency, and achieving simplicity of operation and control. The operation provided valuable information on process scale up parameters, process control strategies, and materials of construction., Several process variables such as bed temperature, solution composition, solution feeding system, bed particle size distribution, and fines recycle system were investigated to determine their effects on process efficiency and the physical and chemical characteristics of the product.

Jan 1, 1985

By J. Y. Hwang

Microwave heating is an attractive alternative to conventional heating methods because heat is generated directly within the microwave absorbing materials. It has potential to be utilized for selective heating and removal of specified components from a materials mixture. This investigation was undertaken to explore the potential of selective heating and burning of binders for foundry sand reclamation. Selected raw materials and binders used in foundry operations were tested to determine their receptivity to microwave heating. Time needed to reach 600°C and/or the maximum temperature achieved for samples irradiated by microwaves for twenty minutes under 800 W microwave power are reported. The microwave heating characteristics of the selected materials are summarized and discussed. The interactions between microwaves and the raw materials used in a foundry. such as silica sand. chromite sand and bentonite (clay) binder were studied. The results showed that chromite sand coupled well with microwave energy at ambient temperature while silica sand did not. This was expected because the major component of chromite sand. iron chromite (FeCr2O4). is a good microwave absorber. while quartz, which is the major component of silica sand, is a microwave transparent material at ambient temperature. Bentonite absorbs microwaves well because it contains a hydroxyl functional group and water molecules in its structure. It was found that the structure of bentonite was changed through microwave irradiation. Microwave heating characteristics of silica sand mixed with different amounts of bentonite binders were investigated. The presence of bentonite in the mixture improved the microwave heating of silica sand significantly. and bentonite was deactivated by the microwave processing.

Jan 1, 1995

By Joseph Bloch

The hydriding of bulk metals and alloys is a gas-solid reaction in which a hydride product layer is initially nucleated adjacent to the gas-solid interface and continues to grow until a complete transformation of the parent (a) phase into the hydride phase. The combination of measurements of the overall hydriding kinetics of samples having defined shapes and dimensions, together with examinations of partially hydrided samples, enables the presentation of the reaction rate in terms of an appropriate reaction model. A common and important type of topochemical development of the hydride in bulk metals and alloys involves a hydride layer formed on the metallic surface. The continuity of the layer can affect the reaction rate. The rate of hydrogen absorption in a sample, in the presence of a hydride layer, is usually analyzed using a model combining several sequential steps in which the hydrogen is transferred from the gas phase into the reaction site. Coupling the flux equations across the layer under proper steady state conditions, results in a complex rate equation in which the steady state rate of hydrogen absorption (proportional to the hydride layer velocity) is expressed in terms of the pressure, temperature, the rate constants of the sequential steps and the critical concentrations of hydrogen in the hydride. Generally, the rate constants of the individual microscopic processes are comparable in magnitude, so that the overall rate is not controlled by any of the specific sequential steps. However, there are two limit cases related to the first stage, the adsorption, for which the general rate equation is much simpler, namely, the fast and the slow adsorption approximations. Using this limit cases, equations are derived for the steady state hydriding rate of a given system. These equations provide means to anticipate the pressure dependence of the steady state absorption rate under low pressures, close to Peq and under very high pressures. At the low pressure regime both the fast and slow absorption cases yield linear pressure dependence. For the very high pressure range, it is found that the rate become independent of the applied pressure. The rate is given then by a combination of the individual rate constants of the system and the critical hydrogen concentrations. The model is shown to apply in several real cases, such as ZrCo, LaNi5 and titanium.

Jan 1, 2002

By L. A. Neumeier

The Bureau of Mines, U.S. Department of the Interior, is investigating the feasibility of partitioning complex sulfide minerals to simpler sulfide .phases by sulfldation reactions. Such partitioning can afford opportunity to improve selective extraction of mineral constituents of value. This report describes initial research involving sulfidation partitioning of chalcopyrite concentrates. Small chalcopyrite samples were sulfidized with elemental sulfur in glass capsules sealed after evacuating and backfilling with helium, by heating for 1 to 24 h at specific temperatures in the range of 250° to 500° C. which extends from below to above the boiling point of sulfur (-445° C). Above the boiling point of sulfur, the overall reaction with adequate sulfur (13.9 wt pct of CuFeS2) is 5CuFeS2 + 4S g ? Cu5FeS6 + 4FeS2.

Jan 1, 1989

By Basant L. Tiwari

An electrolytic process, based on a three-layer concentration cell, to extract magnesium from commercial aluminum alloy scrap has been examined. The process was repeatedly tested at 1025 K with two cells of d1fferent sizes, 0.6 kg and 5 kg feed aluminum, to have a better understanding of the opera ting parameters and evaluate the scale-up potential. In both cells, the magnesium content of the scrap was selectively reduced ?from 1. 1 to less than 0.1 wt.% at anodic current dens-Hy as high as 1. 1 A/cm2 with current efficiency exceeding 85%. Magnesium was recovered in the form of salt coated globules. Comparison of performances for the two cells suggests that the process can be scaled up. With further development, this process could become a viable alternative for demagging secondary aluminum.

Jan 1, 1985

By A. A. el-Geassy

High-grade iron ore fines rejected from the DRl plants (>96%Fe20) were isothermally reduced in 30-60%COIH2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either H2/CO or H2/CO/S mixtures at 823-1073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduction mechanism, The influence of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization reaction under the different experimental conditions.

Jan 1, 2003

By R. M. Taylor

Lime addition to acid mine drainage (AMD) leads to precipitation, predominantly of metal hydroxides and calcium sulfate, and is the benchmark for remediation by precipitation. Geo2 Limited of Melbourne, Australia has developed and patented a novel alternative precipitation scheme based on the formation of mixed valency, M(I1)-M(III), hydroxide sulfate salts. When the composition of AMD is appropriate, the Green Precipitate Process provides a useful and more effective alternative to conventional liming. The characteristics and utility of the Green Precipitate Process are described in terms of the underlying chemistry, and a case study where the Green Precipitate process outperforms conventional liming. A mobile pilot pipe reactor rig which was built by Geo2 to demonstrate the process, and used successfully in both Australia and the United States, is described.

Jan 1, 1998

By D. L. Yopps

Platinum-group metal (PGM) flotation .. concentrate from the Stillwater Complex, MT, was subjected to biooxidation using Thiobacillus ferrooxidans in an effort to break down the sulfide minerals and liberate the ? associated PGM's for subsequent chemical leaching. Bacterial treatment oxidized up to 94 pct of the sulfide present, destroyed the PGM-bearing pentlandite [ (Ni,Fe),9Ss) mineralization, and dissolved most of the nickel in the concentrate. Results showed that increased sulfide oxidation during the biological stage led to improved PGH recovery in the subsequent. chemical leaching stage. cyanidation at 80° c proved to be the best chemical leachant tested. It removed 7.6 pct of the palladium, 94 pct of the rhodium, 97 pct of the gold, but only 34 pct of the platinum from the biooxidized concentrate.

Jan 1, 1991

By H. L. Fraser

A review of the possibilities of performing microchemical analysis in thin sections using a combination of scanning transmission electron microscopy and energy dispersive spectroscopy of x-rays is given. Particular attention is paid to the factors that limit accurate analysis at the highest spatial resolution. As an example of the use of these techniques applied to a potential problem in minerals processing, the identification of iron pyrite and pyrrhotite particles in Illinois, Herrin #6 coal is presented.

Jan 1, 1981

By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

By F. Elgersma

A high purity electrolysis solution is essential for hydrometallurgical zinc winning processes. For this reason ferric iron containing compounds such as jarosite are precipitated as iron and impurity collector during the calcine leaching. Jarosite thus forms a chemical waste and creates environmental problems. This research contributes to the development of a wet jarosite treatment process, where less contaminated jarosite is produced which can act as an iron source. The present work studies jarosite precipitation kinetics and the uptake of zinc cations in batch and continuous experiments. The distribution coefficient for zinc in continuous experiments is constant for a wide ratio of zinc over ferric ions in the solution. Addition of NH, + ions in batch experiments accelerates the conversion rate equivalent to the driving force increment. Addition of 50,2-ions above the stoichiometric ratio increases the conversion rate less then could be expected from the increase in the estimated driving force. Zinc ions tend to retard the conversion rate. An increasing reaction temperature increases the conversion rate. Below 75 ?C the conversion rate approximates zero.

Jan 1, 1990

By Animesh Jha, Chris Dometakis

"Without the use of a flux, only a poor dispersion of ceramic phase can be achieved. A molten-flux-assisted ceramic phase dispersion technique for producing aluminium alloy metalmatrix composites has been developed. In this paper, we report the physical chemistry for the dispersion of TiB2 in molten aluminium. In particular, aspects of the interfacial energy and the thermodynamics of the dispersion reactions are briefly discussed for enhancing the volume of dispersion phase in the molten metal and for controlling their morphology. This investigation also addresses the role of molten flux in the fabrication of AI-alloy mmc using a casting technique. The morphological aspects of the dispersion are explained on the basis of the classical theory· of nucleation.IntroductionMetal matrix composites (MMCs), have long been recognised as an important class of material due to their greater wear resistance, specific stiffness and temperature capability when compared to conventional monolithic alloys. Particulate reinforced composites produced by melt casting techniques have been amongst the first MMCs to achieve commercial market viability. The advent of melt mixing techniques such as the Duralcan™ process have enabled low cost, easily fabricated composites based on the AI-SiC and AIAlz0 3 systems to be produced. In this process, uncoated ceramic particles with diameters 10ltm and larger, are incorporated into conventional monolithic alloys with reinforcement levels up to 25 volume percent. The AI-7Si-SiC metal-matrix composites have good wear resistance, high strength, low density and high thermal conductivity. The combination of these physical and mechanical properties has become a major attraction for the fabrication of light-alloy composite disc rotor brakes for the automotive sector2. However, in silicon-free alloys, SiC is thermodynamically unstable above the composite melting point and is extensively attacked by the melt to form aluminium carbide3 :"

Jan 1, 1996

By K. J. Cathro

A hydrometallurgical process is described for the recovery of copper from chalcopyrite concentrates. The process is based on a cupric chloride leach, the concentrate having first been "activated" by heating it with sulphur at a temperature near 400°C. This activation process converts most of the iron of the chalcopyrite to pyrite, which is insoluble in the cupric chloride leachant. The copper is converted to the mineral idaite, which dissolves readily in hot cupric chloride: at 106°C, 98% of the copper is extracted in a three-stage countercurrent leach, the leaching tirqe being 1 hour per stage. The sulphur of the chalcopyrite appears as elemental sulphur, which is recycled for the activation of further concentrate, the final leach residue consisting of pyrite, plus the gangue present in the original concentrate. The copper extracted can be recovered by electrowinning, using a diaphragm cell. Current efficiency (one-electron basis) is about 70% but the cell voltage is only about 1 V, so that power consumption is three times lower than for the conventional sulphate electrowinning process. The leachant is simultaneously regenerated in the anode compartment. The behaviour of minor elements in the concentrate has also been studied.

Jan 1, 1976

Based on experimental and computer simulation results from our group, we report a systematic, atomic level analysis of carbon dissolution from carbonaceous materials in molten iron. Experimental results on graphite / Fe-C-S system were obtained using carbon dissolution studies, XRD and FESEM investigations and were supplemented with Monte Carlo simulations. Three basic mechanisms, namely carbon atom dissociation rate, interfacial phenomena and mass transfer in the melt were found to be responsible for the overall dissolution process. While mass transfer in the melt is governed by the concentration gradients, melt composition and temperature; impurities present in ash play a significant role in the interfacial phenomena. For less ordered forms of carbonaceous materials, carbon atom dissociation rate depends strongly on the degree of long-range order and is an important rate controlling mechanism in the overall dissolution process. A systematic comparison of dissolution rates for a variety of coal-chars, natural and synthetic graphites has been carried out in an attempt to identify rate-controlling mechanisms. The structure of the carbonaceous material appears to be an important underlying factor in the carbon dissolution process.

Jan 1, 2003

By Veena Sahajwalla

The cupola furnace is a coke-fueled shaft furnace used as a primary melting unit in iron foundries. Control of chemical composition of the iron tapped from the cupola is a key factor in productivity and quality control. In an effort to develop a control model for the cupola, a fundamental approach based on physical and chemical principles has been taken to describe the melting process. The behavior of oxidation of the solid charge in the stack of the cupola has been studied. Sulfidation of the charge materials by sulfur-bearing components released to the furnace gases from the coke has been described. Carburization of metal droplets of iron and of steel in separate molten streams has been characterized. Finally, reactions with alloying elements in the hearth (well) of the furnace have been defined. These reactions have been described in a computer-implemented model developed to predict the composition of the iron tapped from the cupola. The model has utilized the thermodynamics and kinetics of the oxidation, sulfidation, and carburization reactions, including temperature and physical aspects, in the various zones of the melting unit. The model predictions have been compared favorably with operating results.

Jan 1, 1992

By James C. Barker

Recent investigations of a 55-km long trend of intrusive complexes on southern Prince of Wales Island have identified significant resources of Nb, Y, REE. U, Zr, and a host of potential by-product metals. The northwesterly trend comprises multi-phased sodic alkaline and peralkaline diorite, monzonite, syenite, and riebeckite granite. There are at least three significant deposit types recognized, two of which, 1) pegmatite dikes/vein-dikes that zone laterally from the intrusions and 2) concentrically zoned pegmatites, contain most of the lithophile metals. A third, epigenetic replacement-type mineralization, contains much of the U resource. Other deposit types with minor or unknown resource potential include diatremes, carbonatite, and placers. This report summarizes the deposit evaluations, characterizes the mineralization, and estimates the resources. To date a total of 40.7 million tons of mineralized material is estimated as indicated or inferred. Most of the Y203 plus REO is at a grade exceeding 0.5% and half of the Nb20S exceeds 0.125%. Tonnage estimates would likely be substantially lncreased with additional exploration. Mineralogy is generally fine-grained and complex, and consists of more than a dozen principal REE-Y-Nb-U-Th-Zr phases, the sum of which may compose up to half of the rock. Approximately half of the REE-Y content comprises the heavy yttrium subgroup which is uncommon compared to deposits elsewhere. Although the Alaskan deposits are likely subeconomic at today's metal prices and consumption levels. recent technological advances suggest future demand may increase.

Jan 1, 1988

By G. R. Palmer

The success of future electric vehicles will depend greatly upon the power supply choices made today. Research is presently being conducted by automotive engineers and electrochemists to determine what battery type may be the most promising. Not only are product production and application efficiencies being evaluated but also environmental concerns of reclamation and recycling. Rechargeable batteries using nickel-metal hydride electrodes are strong candidates for these electric vehicle applications. The U.S. Bureau of Mines is investigating hydrometallurgical technology that separates and recovers purified metallic components present in nickel-metal hydride battery scrap. Sulfuric, hydrochloric, and nitric acids are all capable of dissolving the battery electrode alloys given the proper operating conditions. Solvent extraction of the leach solutions using D2EHPA removes iron, and selective precipitation shows promise of recovering the other metals in the H2SO4 and HNO, systems.

Jan 1, 1994

By Suresh Sundarraj

A diffusion mass transport model for predicting the microsegregation in a solidifying and coarsening dendritic mushy region of a binary alloy is presented. Two versions of this model are tested; one based on expressing the solute concentration in terms of mole fraction and the other on expressing the solute concentration in terms of mass fraction. On comparing previous model data sets and conditions, used in the analysis of Aluminum-Copper systems, a number of inconsistencies emerge. These inconsistencies are resolved on identifying a single set of data and conditions which take account of compositional density changes, "non-linear" thermodynamics and dynamic coarsening. An additional investigation is carried out to study the effect of assumed cooling mechanisms.

Jan 1, 1992