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By S. Seetharaman

A mathematical model has been developed to evaluate the viscosities of melts at high temperatures. The viscous flow in liquid is described by the equation, {n = Aexp(AG*/RT)} based on the absolute reaction rate theory. The Gibbs energy of activation,{ AG* } is considered to be a function of the temperature as well as the composition of the melt. The model has been applied successfully to various metallic and slag systems from unary to quaternary. On the basis of this model, a relationship has been suggested to relate the Gibbs activation energy of viscosity to the Gibbs energy of mixing in binary metallic melts. The viscosities predicted from available thermodynamic data in the case of a number of binary metallic systems using this correlation show satisfactory agreement with the reported experimental values.

Jan 1, 1994

By Seetharama C. Deevi, Mohammad R. Hajaligol, Sarojini Deevi

"Carbides and nitrides of iron are being considered as magnetic materials for high-density recording due to their chemical stability and high-saturation magnetization values (> 100 emu/g). Iron carbides and iron nitrides with magnetic properties suitable for magnetic media were synthesized by employing a novel synthesis procedure based on fluidization of powders in reactive atmospheres. Fluidized-bed reactors of laboratory, bench, and pilot scale were employed for the synthesis of iron carbide, FeSC2, by reducing and carburizing U-Fe203 in the temperature range of 300 to 550 ºC. A temperature of 400· ºC and a reaction time of 2 to 3 h are found to be optimal for the synthesis of iron carbide. When the carburization was carried out in a reducing and carburizing atmosphere such as carbon monoxide, nucleation and growth of FeSC2 occurred directly from Fe304 with no intermediate phases such as FeO or Fe. Longer carburization times resulted in the deposition of carbon on the surfaces of FeSC2 particles due to Boudouard reaction, and higher temperatures favored the formation of a mixture of carbides such as FesC2 and Fe3C. Iron nitrides were synthesized by reducing u-Fe203 in the temperature range of 350 to 550 ºC, followed by nitriding in the temperature range of 350 to 550·ºC. The powders were characterized using X-ray diffraction, scanning electron microscopy, thermogravimetric analyzer, and a vibrating sample magnetometer.IntroductionRecent demand for high-quality recording of optical, electrical, and audio signals generated interest in magnetic tapes with high-recording densities as compared to the conventional magnetic tapes based on U-Fe203. At present, commercially available magnetic tapes contain maghematite, U-Fe203, as a magnetic material with a saturation magnetization of90 emu/g and a coercive force of 400 Oe. Recording of signals at a higher density per unit volume of magnetic material demands magnetic materials with high-saturation magnetization and a reasonable coercive force. Although metallic iron particles possess a saturation magnetization of 130 to 150 emu/g and a high coercive force of 1000 Oe, the gradual oxidation of iron-to-iron oxides (of lower saturation magnetization) prevents the use of iron particles for high-density recording. In contrast, iron carbides such as FesC2, Fe7C3 and iron nitrides such as Fe4N and Fe3N possess excellent magnetic properties coupled with good electrical conductivities and high hardness. The carbides and nitrides of iron have generated significant interest as magnetic materials for the next generation of magnetic tapes due to their unique magnetic properties and relatively greater oxidation resistance as compared to metallic iron particles [1-4]."

Jan 1, 1994

By William R. Opie

Considerable effort by extractive metallurgical research organizations has been devoted recently to developing pollution-free processes for treating copper sulfide concentrates. A number of hydrometallurgical processes are in various stages of development and have been subjected to economic evaluation. Although the hydrometallurgical approaches eliminate SO2 emission problems, they create objectionable effluents and residues, make precious metals recovery complex, and are not very efficient for treating chalcopyrite. Furthermore, they are consumers of considerably more energy than pyrometallurgical processes which produce blister copper that can be electrorefined to commercial grade cathodes. This paper discusses a pyrometallurgical process under development by AMAX Base Metals Research & Development, Inc. (1) The original objectives set for the process development were: 1. Sulfur control of at least 95% with elimination of fugitive emissions. 2. Copper and precious metal recoveries as good as or better than conventional processes. 3. Low capital cost. 4. Competitive operating costs 5. Use of known proven technology where applicable.

Jan 1, 1976

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

By E. J. Peterson

Oil shale retorting induces mineral and chemical reactions to occur on the macroscopic and microscopic levels in the kerogen-bearing marlstone. The nature and extent of the reactions is dependent upon process variables such as maximum temperature, time at temperature, atmosphere, and raw shale composition. This report describes the investigation of the mineral, chemical, and trace element release properties of spent shales retrieved from an experimental in situ retort at Occidental Oil Shale, Inc. 's Logan Wash site in Garfield County, Colorado. Correlation between mineralogy of the spent materials and the mobility of major, minor, and trace elements are indicated, and relationships with important process parameters are discussed. The progress .of carbonate decomposition reactions and silicat ion reactions is indicative of the processing conditions experienced by the shale materials and influences the mobility of major, minor, and trace elements when the solids are contacted by water. Shale minerals that are exposed to the extreme conditions reached in underground retorting form high temperature product phases including akermanite-gehlenite and diopside-augite solid solutions, kalsilite, monticellite, and forsterite. The persistence of relatively thermally stable phases, such as quartz, orthoclase, and albite provide insight into the extremes of processing conditions experienced by the spent shales. Leachate compositions suggest that several trace elements, including vanadium, boron, fluoride, and arsenic are not rendered immobile by the formation of the high-temperature silicate produce phase akermanite-gehlenite.

Jan 1, 1981

By C. P. Manning

This paper reports recent progress in the development of a unique metal extraction technology utilizing zirconia-based inert anodes for the electrolytic reduction of metals from their oxides. In this process, the target metal oxide is dissolved in an ionically conducting liquid solvent phase. An extended anode consisting of an oxygen-ion-conducting stabilized zirconia membrane in intimate contact with a catalytically active electronic phase and an inert electronically conducting cathode are inserted into the molten flux containing the oxide. When the appropriate electric potential is applied between the electrodes the target metal is reduced at the cathode and oxygen ions are selectively transported across the stabilized zirconia membrane and oxidized at the anode. When the process is conducted at temperatures between 1200-1400°C, the ohmic resistance drop across the stabilized zirconia membrane is low, and high current densities on the order of I A/cm2 or greater can be obtained. In addition, the process efficiency can be increased further by directly reforming hydrocarbon fuel over the anode. Laboratory experiments at Boston University have demonstrated the technical viability of employing zirconia-based inert anodes for environmentally sound production of metals such as magnesium, tantalum, aluminum, etc., directly from their oxides. Significant progress has been made in the application of this concept to the electrolytic reduction of magnesium at 1300°C. The research topics covered include stability of the zirconia membrane in the selected molten solvent (flux), volatility of the flux, electrochemical characterization of the electrolytic cell, and analysis of the metals produced.

Jan 1, 2003

By S. E. Khalafalla

A method for preparing ferrochromium alloys containing less than 2 pct carbon has been devised in a single vacuum furnace reactor. This method can conserve chromium and should reduce the capital and energy requirements relative to chromite electrothermal reduction. Reduced products containing less than 2 and as low as 0.01 wt pct carbon were obtained by reacting pellets of chromite and carbonaceous reductant mixtures at pressures of 0.1 to 1 ton and temperatures of 1,230° to 1,320° C. The extent of reduction increased with increased temperature and decreased pressure; however, operating conditions were limited due to the onset of significant chromium vaporization at higher temperatures and lower pressures. Foundry coke, anthracite, and carbon black were found to be superior to graphite as reductants. The reduction of chromite to metallics was found to proceed via the carbide intermediates Fe3C or Cr3C2. Lime accelerates the. rate of solid state reduction of chromite and can shorten the furnacin1r time at 1,3000 C under vacuum from 13 hours to less than three hours. Additional lime and silica are added to the hot reduced chromite after releasing the vacuum and raising the furnace. temperature to 1, 700° C. Soaking the charge for about 20 minutes gave a button of low carbon ferrochromium alloy beneath a well-defined slag layer.

Jan 1, 1985

By Robert Mensah-Biney

The loading characteristics of gold-tetrabromide species onto a weak-base resin, PAZ-4, were evaluated using a completely mixed batch reaction system. The time. to attain equilibrium loading was substantial, on the order of several days. However, abnormally high loading capacity values of 15 to 20 meq Au/g dry resin (1000 to 1300 kgAu/tonne) were attainable in 24 hours. The loading of gold-bromo species by P AZ-4 was visualized as consisting of two processes: (i) the rapid adsorption of [AuBr4r species by simple ion exchange mechanisms and (ii) reduction of [AuBr4r to metallic gold by an electron exchange mechanism. Elution of gold from loaded resin was feasible provided the resin had not been loaded to high capacity values. If loading is carried to high levels, complete elution becomes impractical and the gold may be recovered by ashing the loaded resin. For the high loading capacities observed this option would appear to be cost effective.

Jan 1, 1991

By H. Y. Sohn

"The nonferrous production industry has gone through a remarkable transformation in recent years in terms of developing and adopting new technologies. Technology innovations have largely been driven by the need for greatly improved environmental protection in addition to increased productivity. One of the most notable aspects of the new technologies is their ability to reduce the emission of sulfur and other pollutants to extremely low levels.The current industry trends towards more environmentally friendly technologies are bringing about additional benefits of developing more efficient, technically advanced, and continuous processes in closed reactor vessels. Key aspects of these modem trends include the use of increased oxygen enrichment in the process gas, better process control, reduced manpower requirements, and plant operations with more skilled personnel.Computer simulation and modeling of complex processes have become more reliable, realistic, and thus increasingly useful in metal production. Some of the notable examples are reviewed.Finally, the need and advantages for value-added production in the nonferrous industry are discussed.I. IntroductionMost recently commissioned technologies for nonferrous metals production have been developed largely in response to environmental concerns. One of the most remarkable improvements made by the nonferrous industry in the last decade has been the rapid increase in sulfur capture. Before the start of the last decade, 90% capture of sulfur was considered good. Since then, strict emission regulations have become the norm in advanced societies, although smelters in many parts of the world still operate with limited pollution control. Other emissions and discharges have also been substantially reduced, resulting in much improved working conditions and worker hygiene in addition to the overall environmental protection. The development of the more environmentally friendly technologies has accompanied other advantageous advances made in the nonferrous industry, i.e., the trend towards more gas-tight, continuous processes and larger plants. This has increased the competitive edge enjoyed by the industry in the industrial countries, offsetting the higher costs of labor and pollution abatement that they have to overcome in those countries. Experience has shown that clean technology often leads to a profitable business, because its adoption forces the concomitant advancement of related technologies in addition to the avoidance of penalties imposed by the public on pollution-prone industries. Needless to say, there are other driving forces for new technologies such as reduction of operating and capital costs, improved product quality, and energy considerations in terms of reduced consumption and utilization of readily available sources."

Jan 1, 2000

By Godwin J. Igwe

For soil remediation technology to be effective, a thorough understanding of the interactions between a targeted contaminant and the soil matrix is crucial. Proper selection of remediation technology, based on understanding the bonding/binding characteristics of the soil and contaminant, can often result in significant remediation cost savings. Contaminated soil cleanup is complicated by both the physical nature of the soil formation and the behavior of contaminants introduced into the formation. Contaminants can exist in the subsurface in different phase attached to the soil surfaces, dissolved in the ground water, or occupying pore spaces as a separate gaseous or liquid phase. Contaminants properties and how they exist in the subsurface influence their toxicity, mobility and treatability with different remediation technologies A soil characterization study was performed to provide information for remediation technology selection for an inorganic lead contaminated soil. The soil pH, TCLP analysis, thermogravimetric analysis, the soluble anions and cations present, equilibrium leaching tests, analysis by x-ray fluorescence, sequential extractions and speciation analysis using scanning electron microscopy, were all used. Results provided many insights into contaminant behavior in the soil, indicating ultimately whether soil washing or solidification/ stabilization remediation technologies were applicable.

Jan 1, 1994

By Z. M. Zheng

Cyclic voltammetry, potential step, and ac impedance techniques were applied to study the electrochemical reaction of arsenopyrite in chloride solutions. The relationship between anodic current density and time in potential step measurements indicates that the oxidation of arsenopyrite is irreversible. The results of the constant potential coulometry show that the stoichiometric factor of the total electron involved in the overall reaction is 14. It is proposed that the dissolution of arsenopyrite is retarded by coverage of sulfur produced in the reaction as an intermediate product. The measured results of ac impedance strongly support the proposition. The proposed reaction mechanism also explains satisfactorily the charging current density and Tafel slopes measured in potential step measurements.

Jan 1, 1995

By P. A. Metz

The Fairbanks mining district has produced in excess of 7.5 million troy ounces of placer gold and 250,000 troy ounces of lode gold since gold was discovered in the area in 1902. The Fairbanks mining district is in the northwestern part of the Yukon-Tanana Upland Schist Terrane, an area of approximately 240,000 square km that has produced in excess of 21 million troy ounces of placer gold. All lode gold production from the terrane has been from the Fairbanks mining district, and all of this production has come from high-grade gold-quartz polymetallic sulfide veins. Gold grains in the vein systems range in size from several microns to several millimeters. The veins are localized in a complex metamorphic rock assemblage which includes greenstones and felsic metavolcanic and volcaniclastic rocks, meta-exhalatives and metasediments. Gold occurs in the metamorphic host rocks in association with arsenopyrite and arsenic-antimony sulfides which occur in lenses and disseminations within the host rock. Gold grains occurring in the metamorphic host rocks range. in size from sub-micron to a few microns in diameter.

Jan 1, 1987

By I. Gaballah

About forty percent of the SOx emissions are generated during the processing of metal sulfides of Cu, Pb, Zn, Ni, etc. Although new technologies for metal sulfide's smelting allow the production of H2S04 with a reasonable cost and decrease the emissions of sulfur oxides, the generated quantity of SOx is considered as a serious threat to environment. This paper suggests alternatives for low temperature processing of complex sulfide ores or concentrates 'CSO or CSC' under neutral, reducing and chlorinating atmospheres or their combination. At T > 400 "C, The neutral and reducing treatments allow the decomposition of pyrite and the partial recovery of sulfur as So and H2S. At 300 "C, the chlorinating treatment of CSC is fast, exothermic and allows the separation of FeC13 from the valuable elements' chlorides. It also generates SyCIx that can be either reduced by H2 or hydrolyzed in presence of sodium sulfide. The recovery rate of elemental sulfur with respect to the sulfur input exceeds 90 %.

Jan 1, 1999

By N. A. Barcza

DC plasma-arc technology using a hollow graphite electrode (cathode) has been successfully implemented in the primary metallurgical industry in South Africa up to the 30 MW scale. Mintek has applied its expertise base, established over the past fifteen years, to testing the treatment of metallurgical wastes such as carbon- and stainless-steel plant dusts, lead- and zinc-containing slags, and residues from the base-metal industry. Favourable results have been achieved, and disposable products were produced. The evaluation of numerous wastes indicates that recovery of zinc as metal gives the best economic return from these sources. Direct recovery via a splash condenser or electrolytic zinc extraction from fume are the two preferred alternatives under review. In both instances dehalogenation is an important issue, but can be achieved by suitable treatment processes. The Enviroplas technology provides a flexible, commercially viable approach to the treatment of a wide variety of wastes. Mintek, together with its associate Pyromet CC, are installing a plasma- arc pilot-plant facility with both an ISP lead-splash condenser of about 5 t/d condensed zinc capacity and a combustion chamber to burn zinc vapour to zinc oxide. This will demonstrate the suitability of the Enviroplas technology for treating specific metallurgical wastes, so that customized industrial plants can be engineered based on large-scale testwork.

Jan 1, 1994

By B. Mishra, W. A. Averill

"The application of various hydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, ego metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been investigated and suggested for dealing with some of these wastes and scrap material.The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EM] and decontamination and decommissioning [D&D].IntroductionThe high temperature carbothermic or metallothermic smelting reduction methods for metal production are associated with the generation of significant quantity of waste as slags, flue dusts, sludges, residues, effluent salts etc. Certain hydrometallurgical processes also generate lots of aqueous waste due to the inherent nature of the technique. Also, the gas-based reduction processes are not applicable to many stable metal compounds, such as alumina, titania, beryllia, lanthanide and actinide oxides, etc. due to thermodynamic considerations. All these methods cause substantial environmental hazard. There is a need to develop alternative processes which have low waste or ideally a ""zero-waste"" generation.Pyrochemical processes using molten salts provide a unique opportunity for the extraction and refining of many reactive and valuable metals either directly from the beneficiated ore (aluminum, beryllium, neodymium, plutonium, uranium, etc.) or from other process effluent that contain reactive metal compounds. The processes reduce metal compounds electrolytically (A12O 3 and BeCI2) on a carbon anode or by calciothermic reduction (Po, Nd). The by-product, in the latter case, is a calcium oxide saturated halide salt. The waste-treatment to recycle the halide has to be done as a separate step or stored as a contaminated waste. A successful separation technology can provide a new insight to the waste minimization strategy for the nuclear industry."

Jan 1, 1996

By C. A. Young, J. D. Miller

Adsorption isotherms previously determined by in-situ Fourier transform infrared/internal reflection spectroscopy (FT-IR/IRS) for oleate adsorption at calcite and fluorite surfaces near pH 9 and at various temperatures are compared. Results indicate that, at both mineral surfaces, chemisorption occurs at equilibrium concentrations below approximately l x l0-5 M oleate while calcium dioleate surface precipitation occurs at higher equilibrium oleate concentrations. The extent of chemisorption at the calcite surface is 3 to 5 times less than that at the fluorite surface while the extent of calcium dioleate surface precipitation on calcite is nearly a magnitude larger than that on fluorite. However, for both minerals, surface precipitation decreases with increasing chemisorption. Contact angle measurements and flotation recoveries show the hydrophobicity of fluorite to be greater than that of calcite at each of the temperatures and oleate concentrations studied. Significant differences are noted only in the chemisorption region. Unlike calcite, the hydrophobicity of fluorite was sensitive to the presence of oxygen in the system. Multichannel Laser Raman Spectroscopy (MLRS) showed this behavior was caused by the double-bond reactivity of adjacent chemisorbed oleate molecules and subsequent formation of an epoxide/polyether complex at the fluorite surface. Such a reaction product could not be detected at the calcite surface. These differences in adsorption density, hydrophobicity, and polymerization behavior are discussed in terms of the intrinsic surface properties of the minerals.

Jan 1, 1999

By Jeffrey W. Braithwaite

The laboratory characterization of the oxidation of chalcopyrite under conditions of deep solution mining is presented in this paper. A salient feature of this system is the pH buffering effect resulting from simultaneous acid producing and acid consuming oxidation reactions. The solution chemistry and related sulfur partitioning of the oxidation reactions are detailed. The contribution of temperature, acid concentration, oxygen pressure, particle size, and solution additions to the kinetics of copper extraction are presented. A mixed kinetic model was used to describe the kinetics of oxidation.

Jan 1, 1976

By Kirsi M. Riihilahti

The oxidation characteristics of solid copper matte particles under simulated Kennecott-Outokumpu Flash Converting conditions are presented. This project is concerned with the determination of the effects of operating variables on the reaction of the particles. Experiments were carried out in a large laboratory-scale flash furnace with 72 wt-% Cu matte by varying initial particle size, temperature, oxygen partial pressure, oxygen-to-matte mass ratio and residence time. Chemical analysis was used to study the oxidation extent and copper volatilization. Particle fragmentation was examined. Fractional conversion and sulfur removal slightly decreased with initial particle size, while a higher oxygen-to-matte mass ratio mainly resulted in higher fractional conversion and more efficient sulfur removal. The fractional conversion values represented the overall extent of oxidation more closely than degree of sulfur removal.

Jan 1, 1997

By J. Brent Hiskey

Recently basic concepts of semiconductor electrochemistry and solid-state electronic structure theory have been applied to the dissolution of mineral electrodes. In this paper, fundamental aspects of semiconductor electro- chemistry and interfacial charge-transfer processes are reviewed. Information regarding the electronic and semiconductor properties of chalcopyrite is summarized. The electrochemical response of chalcopyrite in acidic solution is analyzed in terms of initial dissolution processes. The initial charge- transfer reaction involves the consumption of holes. It has been shorn that Fermi level pinning is consistent with observed electrochemical and dissolution behavior. Semiconductor electrochemistry has proved helpful in explaining the formation of intermediate surface films produced during the initial stages of chalcopyrite dissolution

Jan 1, 1993

By Dan A. Mackie

Cyanide leaching operations have taken a beating from the press and the public at large for its seemingly haphazard approach to control of cyanide solutions and containment of tailings. Major spills in Colorado, Guyana, Spain, and more recently, Romania, have highlighted what had already been perceived to be a bad scene. Citizen initiatives and legislative actions are increasing. Whether these indictments are justified or not will not be debated in this paper. What this paper presents is that the technology to avoid these disasters and future ones has been around for more than ten years but has been ignored by the industry, despite demonstrated' cost effectiveness. It is time for miners to wakeup, and use emerging, instead of old, technologies.

Jan 1, 1998