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By Derek J. Fray

"A need exists for fast and accurate analysis of species in various phases at elevated temperatures. Although modern analytical techniques are very efficient, the equipment is usually situated some distance from the industrial operation and time is spent taking the sample and sending it to the analytical facility. Several minutes can easily lapse and, during this time, heat must be supplied in order to keep the system molten and, if the composition is changing rapidly due to a refining process or reaction with the environment, the information may only be of retrospective use. Perhaps more important reasons for the use of on-line sensors are that instantaneous analysis gives better control, process optimisation and the minimisation of energy losses and pollution. To date oxygen has been the only element which is measured widely using solid electrolytes. However, the analysis of many more elements is required and possible electrolytes for other species are discussed. For some elements, ~here is no suitable conducting electrolyte and, therefore, a different approach is adopted where the electrolyte, in which one species is mobile, comes to equilibrium with another species. IntroductionThere is an ever increasing demand for the development of sensors for on-line measurements in most areas of technology and, in particular, metal processing. This is especially relevant in situations where greater control can be achieved by monitoring the chemical composition of the melt during processing and where a minor constituent in the melt can have a major effect on the properties of the finished alloy. Although modern analytical techniques are fast and reliable, the equipment due to its complexity, is frequently situated away from the process area and valuable time may be spent in sampling and transportation. During this period, heat may have to be supplied to prevent solidification and the refining reactions may be continuing, and, therefore, the analytical information may not be of direct use."

Jan 1, 1988

By William Petruk

The capabilities of SEM/image analyzers for determining quantitative mineral data which have a bearing on extractive metallurgy have given applied mineralogy a new dimension. The capabilities include automatic mineral identification, unattended operation, search for rare minerals, and measurements of (1) mineral quantities, (2) grain and particle size distributions, (3) liberation characteristics of minerals in ground ores, and (4) mineral associations. Data on mineral quantities define the distributions of elements among minerals, provide background information on characteristics of the samples, and provide a data base for a mineral-materials balance. Size analysis data of the minerals in unbroken ores are used to predict the grind required to liberate minerals. Data on liberation analysis can be used in many ways. One application is to process the image analysis data for feed, concentrate and tails by a materials balancing technique to calculate the recovery of liberated and unliberated grains at each point in a circuit. The calculated recovery data define the behaviour of an ore in a concentrator, pilot plant or bench test, and indicate whether recovery improvements are possible and/or feasible for a particular ore.

Jan 1, 1991

By Ann E. Visser

Aqueous Biphasic Systems (ABS) form upon the admixture of certain water-soluble polymers or polymers and salts above critical concentrations, and thus represent liquid/liquid extraction systems whose nature is entirely aqueous. We are currently investigating the utility of ABS (and its solid phase analogs) as "green" alternatives to the use of volatile organic diluents in separations of metal ions. Chaotropic (water-destructuring) metal ions with small negative AGhyd (e.g., Tc04) tend to partition quantitatively to the PEG-rich phase of an ABS, but even hydrated metal cations can be partitioned to the PEG-rich phase if a suitable extractant (e.g., halide, dye, crown ether, etc.) is used to produce a more chaotropic ion-complex.

Jan 1, 1999

By D. Papazoglou

This work was undertaken to investigate the thermodynamic and kinetic feasibility of using hot sulfur dioxide bearing gases from smelting processes to selectively sulfate the nickel in nickel laterite ores for subsequent extraction in water. The environmental benefits ofthis approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the S02 rather than converting it to sulfuric acid are strong drivers for such a process. A thermodynamic analysis indicated that selective sulfation of the nickel could be feasible under appropriate conditions and these were explored through a series of laboratory scale experiments. Laterite samples were reacted at temperatures between 500 and 800°C with an equilibrated mixture of sulfur dioxide, oxygen and nitrogen in a fixed bed reactor. Tests were conducted on saprolitic ore from Bulong, Western Australia, limonitic ore from New Caledonia and garnieritic ore from Indonesia. Nickel extractions were highest from the limonite and relatively low from the other ores. The maximum selective extraction of nickel from the limonite in a single stage sulfation was 73%. Sulfation of other elements present in the laterites was also examined. A two-stage process was also identified which involved sulfation using a strong sulfation potential followed by weaker sulfation potential to attempt to convert ferric sulfate formed in the first stage to ferric oxide. This increased the extraction for the limonite ore to around 84% Ni, 95% Co and 2% Fe. Direct sulfation of laterite could be feasible in locations where sulfide smelting or roasting operations are relatively close to laterite deposits.

Jan 1, 2003

By J. L. Jambor, H. W. Nesbitt

Oxidative dissolution of pyrrhotite and pyrite is largely responsible for the sulfate-rich waters of the vadose zone in the Waite Amulet tailings. Although the shallowest of the sulfate-rich waters are of the Fe-SO4 type, they change to Mg-SO4-type, near-neutral waters within 1-2 m of the tailings surface. Phyllosilicates and amphiboles are the only minerals present in sufficient quantity to ameliorate the amount of acidity produced. X-ray diffraction and microscopic studies of bulk sample indicate that quartz, chlorite, talc, amphiboles, magnetite, albite, and micas are the major and minor non-sulfide minerals, but their variations with depth do not give clear indications of depletion in the vadose zone. Mineralogical and bulk chemical compositions of the tailings confirm that Fe2O 3 has accumulated in large quantity in the vadose zone, with the Fe having been derived from Fe sulfides. When the effect of Fe2O3 is accounted for, the bulk compositions suggest that SiO2 is slightly more abundant in the vadose zone than in the saturated zone. This may be the result of residual enrichment of siliceous minerals such as quartz and albite in the vadose zone. Weathering of the tailings since the cessation of deposition in 1962 has resulted in a well-defined zone of sulfide depletion and secondary sulfate-mineral development. Although some silicate dissolution is indicated by pore-water compositions, the role of silicates in providing neutralization seems to have been minimal. The contribution by silicate minerals in laboratory tests of neutralization potential may be excessive relative to that in natural settings.

Jan 1, 1999

By M Kolbe

Co-Cu exhibits a metastable miscibility gap in the region of the undercooled melt. Specimens have been undercooled and solidified containerlessly into the metastable miscibility gap in an electromagnetic levitation facility (EML) and in drop tube (DT) experiments. Due to the high undercooling the velocity of the solidification front is very high and the microstructure is frozen in instantaneously. The microstructure of samples processed in the EML is influenced by the electromagnetic stirring due to the induction of electrical currents into the melt. A variety of microstructures has been observed. After undercooling below the binodal the liquid melt separates into the Co-rich L1-phase and the Cu-rich L2-phase. Two basic morphologies of the L1-phase can be observed, they can be attributed to the transition in dendrite growth from diffusionally and thermally controlled to only thermally controlled growth. Transient microstructures are observed after solidification in the vicinity of the binodal. Drop tube experiments, which lead to a rapid solidification of a distribution of droplets under reduced gravity conditions, in contrary allow for the observation of the early stages of demixing: the microstructure shows a homogeneous distribution of spherical particles of the minority phase in the droplets. The cooling rate of the droplets and its dependence on the droplet radius has been calculated. The solidification velocity as a function of undercooling has been measured in the EML for the composition Co-lB.Bat%Cu. The data are analysed in the framework of the LKTlBCT model with a velocity-dependent distribution coefficient as well as within a model of Galenko and Danilov using a kinetic growth coefficient of u=0.22 m/Ks.

Jan 1, 2002

By S. J. Macnaughton

The Olympic Dam deposit in South Australia contains 2% copper and 0.06% uranium, which are present as bomite, chalcocite, chalcopyrite, uraninite, coffinite and brannerite. The copper is principally recovered using flotation. The flotation tailings, which contain the bulk of the uranium, and typically 0.3% copper, are leached using sulfuric acid and an oxidant at atmospheric pressure. This paper describes the results from a detailed investigation of the leaching behaviour of this ore. The influence of acid strength, Fe3+ concentration, redox potential and temperature on the dissolution of uranium and copper minerals was studied. Experimental data were obtained from extensive batch leach tests. Mineralogical studies, including SEM analysis of individual mineral grains, were also carried out. The maximum extraction of uranium determined experimentally was in good agreement with that predicted from SEM determination of the proportion of refractory brannerite in the ore. The leaching rate of copper was found to be independent of acidity over the range 20 g L-' to pH 2.0, but was strongly dependent on temperature and Fe3+ concentration. Uranium extraction showed a weak de endence on acidity, Arrhenius temperature dependence and a complex co-dependence on F>+ concentration and redox potential. A kinetic model has been developed, which predicts copper and uranium dissolution. This model will be incorporated into a more comprehensive model that can be used to predict leach performance and reagent consumption for specific ore samples.

Jan 1, 1999

By Renato G. Bautista

"The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.IntroductionThe understanding and the elucidation of the mechanism of the rate phenomena for a specific chemical reaction system is of prime importance in the development of a successful chemical process. The development of successful emerging technologies for metals separation will depend on the accurate interpretation of the intrinsic chemical reaction kinetics and the rate of mass transfer of the desired metal species during its separation from the undesirable chemical species. This is the case whether the process application is for separation, concentration, and /or purification.The chemical processes that will be examined in this presentation will include leaching, solvent extraction, membrane separation, precipitation, and electrodeposition."

Jan 1, 1996

By R. G. Henley

Mount Isa copper concentrate was combusted in a laminar-flow furnace. The conditions simulated those likely to be encountered in flames in flash smelters of the Outokumpu (air as oxidant) and INCO (oxygen as oxidant) types. The range of conditions studied was as follows: T 400-1400°C, 02 0-100%, SO2 0-95% for residence times up to 0.23 s. The distribution of sulfur, arsenic and lead between the particles and the gas phase was studied. Combustion was very rapid provided the concentrate was adequately dispersed, i.e., no agglomerates. The importance of the latter is discussed. It was possible to oxidize 80% of the sulfur present in the con¬centrate after only 0.1 s reaction time at 1000°C in an atmosphere contain¬ing 8.5% 02 and 12.5% SO2. Best volatilizations (90% of the As, 52% of the Pb) were obtained under localized conditions attained in an air-type flame. Average volatilizations were: air-type flame, As 50%, Pb 32%; oxygen-type flame, As 40%, Pb 30%. The substitution of oxygen for air reduced the arsenic volatilization. The products of combustion were mainly cuprospinel and cuprite; small inclusions of elemental copper were found in some of the particles. At high temperatures, there was a loss of copper due to vaporization of CU( g) CuO kg) (g)

Jan 1, 1983

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 Renato G. Bautista

The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions:. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.

Jan 1, 1996

By S. E. James

EAF dust has been listed as a "hazardous waste" due to the presence of lead and cadmium, and at times chromium. The 550,00 tpy production of . .EA]' dust, estimated for the United States alone, contains more than 10,000 tpy of lead and about 250 tpy of cadmium in addition to nearly 1'00,000 tpy zinc. Even though the listing of .EAF dust as a hazardous material stimulated extractive metallurgical work worldwide, process development efforts have focused only on the recycle of the potentially-valuable zinc units. However, the recycle of the lead and cadmium, while not lucrative, is the more critical effort. Horsehead Resource Development Company, Inc. (HRD), in conjunction with its sister company, Zinc Corporation of America (ZCA), has taken a unique approach to total recycle of the toxic heavy metals found in the EAF dust. Impure oxide, produced by either a Waelz kiln or FLAME REACTOR Process and containing the lead and cadmium, is calcined in a rotary kiln at Palmerton, Pennsylvania, to produce a refined zinc-rich intermediate for ZCA's electrothermic zinc plant at Monaca, Pennsylvania. During the calcining operation, lead and cadmium are concentrated in a fume product and shipped to ZCA's electrolytic plant at Bartlesville, Oklahoma. At Bartlesville, a new hydrometallurgical circuit has been constructed and the existing cadmium plant expanded. The combined facilities permit the total recovery of cadmium to refined metal and the lead to .a silver-rich intermediate, which is sold to lead smelters. In this paper the Waelzing, calcining and new leaching facilities will be described.

Jan 1, 1990

By S. J. Thiele, T. Newton, W. Magalhäes, T. Takayama, J. Welsh

Companhia Paraibuna de Metais (CPM) is presently pursuing a zinc production expansion project. Besides increasing production, the goal of the project is to address existing problems while providing a platform for a proposed twofold increase in production in 2003/2004. Therefore, the current expansion strategy was formulated to address present and future requirements. Computer simulation modeling and full scale plant testing are being used to generate data to optimize the operating conditions and to perform a sensitivity analysis. The initial phase of the project, which will boost CPM's capacity to 86,000 t/y of marketable zinc, is to be completed in September 2000.

Jan 1, 2000

By Christopher B. Vierrether

Reflected light microscopy, scanning electron microscopy, and electron microprobe analysis have been used to determine the mineralogy, phase percentages, grain sizes, textures, and partitioning of cobalt and nickel in two cobalt-nickel rich mattes. These mattes were prepared by submerged bath smelting from a flotation cobalt-nickel concentrate containing 4.8% cobalt and 5.1% nickel. The concentrate was derived from lead-zinc-copper ores of the Viburnum Trend, southeast Missouri. Eleven discrete phases have been distinguished in the matte samples, three of which contain significant cobalt and nickel. The phases are cobaltpentlandite ((Co,Ni,Fe)9S8), cobalt-bearing marmatite ((Co,Fe,Zn)S), shandite (Ni3Pb2S2), bornite (Cu5FeS4), galena (PbS), magnetite (Fe3O4), pyrrhotite ((Co,Ni,Cu,Fe)1_xS), chalcocite (Cu2S), CuPbS phase, metallic copper, and metallic silver. Cobaltpentlandite and cobalt-bearing marmatite- occur in coarse grains (50 µm) that would separate readily during grinding, but shandite contains small (5 - 10um), abundant inclusions of pyrrhotite and bornite.. Some mineralogical variations between the two matte samples were due to differing degrees of oxidation during smelting,

Jan 1, 1988

By Omid Marzoughi

Chromium has a wide range of applications, including as an alloy addition in various steels and also as a corrosion resistance coating. Carbothermal reduction of chromite ore (FeCr2O4) in a submerged arc furnace is an important industrial process for extracting chromium, but the energy consumption is excessive. It is suggested that one area for future research is the low temperature carbothermic solid state reduction of chromite to produce an intermediate product, which can subsequently be upgraded to ferrochromium. In this regard, a thermodynamic model has been developed to investigate this process and the effects of temperature, carbon additions and ore composition on the recovery of chromium and the grade of the ferrochromium, have been studied. Further development of the model may allow it to be applied to the simulation of other processes for the recovery of chromium from chromite ores.

By Klaus Bauckhage

Phase-Doppler-anemometry (PDA)-measurements have to be taken from representative measuring positions from inside the spray cone, helping - with the support of simulated data of improved process models - to describe the multiphase flow situations within the spray cone - and accordingly to that - the heat transfer conditions for the rapid cooling and (partly) solidifying melt droplets before their impact onto the substratddeposit. Simulations and PDA-measurements thus give the base to confirm the hypothesis of the existence of a semisolid mixed-layer and it's influence on the resulting material structure during compaction. The dispersed particles in the spray cone exhibit a cooling and solidification process within a split of a second, which leads - as far as the particles solidify - to a dendritic structure with very short dendritic arm spacings. This causes within the particles extremely short distances for the following equalizing diffision processes taking place on a high temperature level (between liquidus and solidus) in the semisolid mixed-layer of the deposit and explaining the short residence times within this zone of only seconds up to a few minutes. This and the fact that the globular structure of the mushy zone (in the semisolid mixed-layer) leads to an unidirectional crystallization process over very short distances also explains the chemical and morphological ,homogeneity of the sprayed material. The dynamics of these process steps, the very special buffer function of the mixing layer during parameter variations as well as the controlled cooling process of the preform in order to avoid hot cracks influence the quality of the material. Due to the necessity of measuring and controlling the particle bound mass-, momentum- and enthalpy- fluxes to the deposit the PDA-technique has been adapted and modified in order to receive in-line and (in the future) also on-line data from the dynamics of the multiphase flow conditions within the spray chamber.

Jan 1, 1999

By M. C. Esposito

Seven pyrite samples purified from coal sources and one ore source pyrite (for comparative purposes) have been characterized by chemical and mineralogical analyses, inherent floatability, apparent specific gravity, surface area, semiconductor type, optical anisotropy, dissolution and oxidation rate. The data clearly demonstrate that pyrites from various coal sources differ not only from ore pyrite but from each other as well.

Jan 1, 1987

By Taufiq Hidayat

Accurate description of complex phase equilibria provide the foundations for the improvement of non-ferrous pyrometallurgical smelting and recycling processes. Recent advances in microanalysis and experimental techniques enable accurate phase equilibria characterisation. Quantitative microanalytical techniques including Electron Probe X-ray Microanalysis and Laser Ablation ICP-MS enable the concentrations of major and minor elements present in different phases in samples to be accurately measured providing data that cannot be obtained using bulk chemical analysis techniques. High-temperature equilibration experiments coupled with the subsequent analysis of elementary reactions at micro- and macro-scales ensure the attainment of equilibrium conditions, and therefore, ensure true phase equilibria information is obtained. Examples of the application of the improved methodology on the investigation of phase equilibria of low-order and complex, multi-component gas/slag/matte/metal/solids Cu2O–PbO–ZnO–Al2O3–CaO–MgO– FeO–Fe2O3–SiO2–S systems and the distribution of minor element are provided. The experimental study is closely integrated with thermodynamic database development for the above system. Example of implementation of the research outcomes into industrial operations is demonstrated.

By P. N. Anyalebechi

The effects of a cross-hatched grooved mold surface topography, casting speed, and superheat on the morphology of solidifying shells of aluminum alloy 3003 have been characterized by a series of immersion tests. The cross-hatched grooves were 0.232 mm deep with wavelength or spacing between 1 mm and 15 mm. The shells solidified at casting speed of less than 10 mm/s on the 1 mm spaced cross-hatched grooved mold surface were fairly uniform with little or no localized variations in thickness. However, the propensity for non-uniform shell growth morphology was exacerbated by an increase in casting speed, melt superheat, and the wavelength of the cross-hatched grooves. This is provisionally attributed to their effects on interfacial heat transfer and wetting of the mold surface by the molten metal.

Jan 1, 2008

By F. D. S. Marquis

An investigation of the mechanisms of formation of two types of porosity-primary and secondary-their characterization, evolution during processing, and effects on the mechanical behavior (fracture, fatigue, and failure) of 7X50 and 2X24 alloys has been conducted. The mechanisms of formation of three forms of primary or cast porosity were investigated, and each form was characterized: (a) macroscopic shrinkage porosity-MSP); (b) microscopic interdendritic porosity (MIP); and (c) hydrogen gas porosity (HGP) or primary hydrogen porosity (PHP). The mechanisms of formation of four forms of secondary or thermal/thermomechanical porosity were investigated, and each form of porosity was characterized: (a) high temperature oxidation (HTO). internal hydrogen precipitation (IHP), or secondary hydrogen precipitation (SHP); (b) preheating blistering porosity (PBP); (c) eutectic melting porosity (EMP);and, (d) dissolution micro void formation (DMF). The evolution and interactions of the primary and secondary types of porosity (w.ith special emphasis on PHP and SHP) during industrial and laboratory processing and their effects on the fracture and failure behavior of both types of alloys (with special focus on fatigue crack initiation and propagation) were investigated.

Jan 1, 1996