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By Mark Tsirlin

Kinetics of the initial oxidation stages of diffusive silicide coatings on 8 molybdenum and niobium at 1100 - 1700 and under the pressure of 400 and 1330 Pa has been studied using methods of gravimetry and gas phase analysis of oxygen, as well as by SEK, XRD and EDMA methods. The first oxidation stage described by asymptotic equation in case of NbSi coating changed over to the stage described by parabolic equation. The asymptotic law was shown to depend on non - stationary conditions on the oxide layer boundaries. Interconnection between silicides and quartz structures, on the one hand, and peculiarities of oxidation kinetics, on the other, is [discussed. The possibility of estimation oxygen atom jump frequency in quartz and fractions of oxygen reacting with metal and with silicon proceeding from the analysis of the kinetic data was ascertained. Conditions of oxidation kine- tics transfer from asymptotic (or parabolic) stage to a non - protective "linear" stage, associated with volatile ~roduct formation, are also discussed.

Jan 1, 1995

By Barry Welch, Kai Grjotheim

"The capital intensive nature of the present process for aluminium smelting, the low productivity per unit reactor, and pressure to reduce the electdcal energy demand have motivated the search for an alternative process. Optional routes include carbo-thennal reduction of alumina (using an alloy phase immediate), chlorination followed by electrolysis of aluminium chloride, and electrolytic decomposition of alumina using inert electrodes. Materials performance and reactor design constraints have been a major limitation for alternatives. However parallel research has led to considerable advances in the process efficiencies and scale of both the Bayer process and the Hall-Heroult cells.Future development of alternatives is dependent on breakthroughs in Materials Science such as the development of stable conducting anodes and stable wettable cathode materials. However if successful it is probable that some spin-offs will be retrofitted to existing cells. Therefore the basic Hall-Heroult technology will continue as the dominant process for at least the next half century.IntroductionThe present Bayer/Hall-Heroult process for production of aluminium is just over 100 years old. Frequently, during the century of its technological development questions have been raised as to whether it is the ideal route for metal production. The questioning was particularly intense in the period between the mid-1950s and the mid-1060s when the limitations of the Hall-Heroult electrolytic stage were evident. Then the cells were only 30 to 35 % efficient with respect to the utilisation of the hydro-electricity (requiring 16 18 kWh/kg, thus making it strongly dependent on cheap electrical energy), while the size of cells being installed were 80 to 130 kA. Hence the process was capital intensive, the productivity per reactor volume low, and the process was labour intensive (requiring about 15 man hours per tonne of aluminium). In addition, the use of pitches for Soderberg anodes and the fluoride electrolyte were creating problems through emission. At that time material science had paid little attention to the manufacture and use of carbonaceous materials or the development of alternatives that were corrosion resistant to cryolite or liquid aluminium. Hence cell lives were short - typically 600 to 1000 days - thus adding to operating costs. Thus the grass over the fence, as foreseen in 1960s vintage crystal balls appeared much greener for alternative processes."

Jan 1, 1988

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 A. Treverrow, G. A. Brooks, H. K. Worner

"The work by H.K Worner and co-workers at CRA in the 1960s, and early 1970s, established that molten metals could be refined continuously utilising counter current flow of metal and slag. Womer also demonstrated that counter current refining could produce highly refined metal products. These developments coincided with the advent of high intensity metallurgical reactors in both the ferrous and non-ferrous industries (e.g. BOS, Q-BOP and later Sirosmelt) that utilised high levels of gas injection to produce rapid stirring and very fast reaction. These new generation of high intensity metallurgical reactors allowed high tonnage rates through relatively small volume vessels.Whilst, it is well known that the counter current flow of reacting phases offers the potential of efficient mass transfer and high purity products, the application of counter current reactors to molten metal/slag systems has been criticized on the basis that they suffer from either low intensity or, alternately, from poor refining due to excessive dispersion. These criticisms relate to the balance between intensity and the refining capacity of a reactor. That is, whilst high levels of mixing transversely to the direction of flow promotes high mass transfer, longitudinal mixing (dispersion) is detrimental to refining. Of course, mixing in one direction invariably leads to mixing in other directions, thus creating a playoff between high mass transfer and excessive dispersion.This balance between intensity and refining has been the subject of recent studies overseas, and at"" the University of Wollongong, using cold modelling techniques to evaluate the effect of mixing on dispersion in a counter current refining launder. These studies have shown that for a given geometry and mixing regime, dispersion decreases with increasing flow of liquid phases. This means that whilst high mass transfer cannot be achieved in a refining launder without sacrificing the degree of refinement, there is no impediment to achieving high productivity through such a system, in fact, high through puts may favour good refining. Thus, it may be possible to match a high productivity smelting operation with a equally productive counter current refining stage."

Jan 1, 1996

By Jagdish C. Agarwal

Although copper ranks very low in the order of abundance of elements in the crust of the earth, it has been one of the first metals utilized by mar, at his emergence from the Stone Age, about 10,000 years ago. Use of copper for weapons, tools, utensils and ornaments dates back to the twilight of history, 6,000-5,000 B.C. Native copper outcrops and the malleability of the metal explain its very early use by the cave-dwellers. The working, melting and extraction of copper from its minerals are among the oldest metallurgical achievements of the human race. The oldest complete smelting installations for the extraction of copper from its minerals, dated about the fourth millenium B.C., were recently discovered in the Timna Valley, Wadi Arabah, Israel. (1) The history of the developments of the extractive metallurgy of copper has been adequately reviewed recently. (2,3) The center of copper production migrated from the Eastern Mediterranean to Northern Europe (Mansfeld, Germany, Swansea, Wales) towards the end of the Middle Ages (1500 A.D.). The production of the metal was boosted tremendously in North America since the end of the nineteenth century (Fig. 1).

Jan 1, 1976

By V. P. Keran

The lead and copper smelting processes employed by Mount Isa Mines Limited, Mount Isa, Australia, are used to illustrate an operating viewpoint of some problems and solutions encountered in existing commercial sulphide smelters. The smelting processes discussed; include updraught sintering, blast furnace and reverberatory smelting, and converting. Selected examples are given of methods implemented, and options available, to improve the productivity and efficiency of conventional smelting processes.

Jan 1, 1983

By A. J. Maselli, E. C. Cemak

Hartford Steel Technologies (HST) has a pyrometallurgical and hydrometaliurgical process capable of reclaiming valuable metals from a hazardous waste· stream such as EAF Dust. The HST Process effectively addresses the growing environmental concerns surrounding the increasing production of EAF Dust without producing any hazardous waste material as byproducts. Currently EAF Dust production levels are exceeding the 1,000,000 metric tons per year mark. The HST Process is designed to separate iron, zinc, lead, cadmium, copper, and silver metals using a two-phased process. The Pyrometallurgical side of the Process utilizes a Rotary Hearth Furnace to separate the iron metal from the remaining metals. These remaining metals are further separated, using a Hydrometallurgical Process, in a series of digestion tanks. The individual metals are then collected in saleable form.

Jan 1, 2000

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 I. Perus, M. Fazarinc, G. Kugler, M. Tercelj

"Ledeburitic tool steels are highly alloyed steels used for specific highly loaded applications but are characterized by low and variable hot workability. In this contribution the importance of selecting the right choice of some essential process parameters, i.e. casting temperature, solidification rate and soaking temperature, needed for improving the intrinsic hot deformability of ledeburitic tool steels, is studied. An inappropriate selection of casting temperature and cooling rate results in precipitation of unusual eutectic carbides that decreases the hot workability, whereas with the selection of appropriate soaking temperature the temperature range of safe hot working can be broadened. For each initial as-cast microstructure individually determined soaking temperature should be selected.IntroductionThe surface cracking during hot deformation of ledeburitic tool steels reduces mechanical properties and their industrial yield. These tool steels have high hardness, wear resistance and high tempering resistance on one hand, and high flow stresses and low hot deformability on the other. Decreased hot deformability of the tool steels is attributed to the type, size, shape, distribution, fraction of eutectic carbides and/or other phases, grain growth, etc. at upper limit while precipitation of secondary carbides and decreased recrystallization rate at lower limit of the safe hot deformation temperature range, [1-6].The occurrence of cracks on most exposed areas of workpiece are related to the areas where similar conditions related to upper and/or lower limit of temperature working range prevail, i.e. areas with accelerated cooling, areas with higher value of accumulated strains where also decreased recrystallization rate with simultaneously presence of higher tensile stresses takes place, furthermore areas of workpiece which are due to combustion conditions in furnace heated to higher temperatures, etc. Thus the areas, where combination of previously mentioned conditions prevails, are more exposed to cracking. This additionally requires that hot deformability of ledeburitic tool steel should be considered as a complex problem. Publications in the literature with regards to hot deformability of tool steels are predominately of a partial nature thus all reasons for unexpected occurrence of cracks are not sufficiently explained in available literature so far. Furthermore modern practice proves that previous processing parameters significantly influence the hot deformability and thus this cannot be considered as a constant value. During heating, soaking and hot deformation various processes take place: decay (decomposition) of carbides, formation of new carbides, dissolution of carbides and of alloying elements, etc. Thus depending on variation of process parameters and chemical composition, that consequently influences the processes related to carbides, shifting of decreased deformability at both limits of temperature working range to higher and/or to lower temperatures can occur, [1-14]."

Jan 1, 2012

By B. R. Baldock

The converting of high-grade nickel matte for production of low-sulphur matte or nickel metal is a process which has eluded metallurgists in the past because of the limitations of conventional converting furnaces. The high temperatures required and the refractory nature of nickel oxide has prevented practical success in a process which has been known to be theoretically feasible for a long time. The Ausmelt top submerged lancing system is capable of operating under close control of the smelting conditions. High temperatures and both rapid oxidation and rapid reduction can be achieved. These features have provided the basis for successful pilot plant trials of the desulphurisation of high-grade matte from the Kalgoorlie Nickel Smelter. Sulphur level in product was lowered from 20 to 25% to as low as 0.2%, with iron levels in matte in the range of 1.0 to 3.5%. The theoretical background of matte desulphurisation is surveyed and the pilot plant operations described. The implications of the results in relation to commercial plants and possible refinery operations are summarised.

Jan 1, 1993

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 Richard B. Diver, Mark D. Allendorf, Daniel E. Dedrick, James E. Miller, Roy E. Hogan, Andrea Ambrosini, Eric N. Coker, Anthony H. McDaniel, Nathan P. Siegel, Gary L. Kellogg

"Converting carbon dioxide and water to hydrocarbons is an attractive option for storing solar energy and, coupled with appropriate CO2 capture technology, for recycling carbon and impacting atmospheric CO2 concentrations. For any process, high solar-to-fuel efficiency is necessary for large scale viability and favorable economics. Thermochemical approaches for solar-to-fuel conversion are potentially highly efficient as they avoid the inherent limitations of photosynthesis and also sidestep the solar-to-electric conversion necessary to drive electrolytic reactions. Solar-driven two-step metal-oxide-based thermochemical cycles for producing the components of syngas, CO and H2, from CO2 and H2O are the basis of the “Sunshine to Petrol” project. Multi-cycle production of both H2 and CO has been demonstrated over several iron- and cerium-based compositions fabricated into monolithic pieces both in the laboratory and at the National Solar Thermal Test Facility. These compositions are being developed for deployment in a unique and continuous solar-driven reactor prototype, the counter-rotating-ring receiver reactor recuperator or CR5.IntroductionThe interconnected challenges posed by increasing global competition for petroleum and the increasing concentration of atmospheric carbon dioxide are now widely recognized. Meeting these challenges requires recognition that although hydrocarbon fuels are ideal energy carriers, they can no longer be thought of as primary energy sources. It is necessary to take the realistic view that our conventional fossil fuels are in fact “stored sunlight” in the form of “sequestered carbon.” This view leads to a search for options to use and store sunlight more directly.Sunshine to PetrolIn combusting hydrocarbons we unlock the energy for utilization, but we also release the carbon to the atmosphere. However, nature teaches us that with an appropriate persistent energy source, e.g. solar irradiation, it is possible to effectively reverse the combustion process and “reenergize” CO2 and H2O back into hydrocarbon form."

Jan 1, 2010

By H. Y. Sohn

The ignition and combustion of chalcopyrite particles under suspension-smelting conditions, in which the particle-particle interaction is neglected, has been analyzed by considering the intrinsic kinetics of oxidation and heat and mass transfer between the particle and its surroundings. Reasonable agreement has been obtained between the calculated results and experimental results from a laminar-flow furnace reported in the literature. This computation- al procedure has further been applied to flash-smelting conditions. Under suspension-smelting conditions (Sh = Nu = 2), chalcopyrite particles ignite at around 960 K. The effects of various parameters, such as oxygen concentration, particle size, and gas temperature, have also been evaluated. Comparison between calculated results in this work and experimental observations indicates that SO is the important gaseous product that forms at the surface of the particle.

Jan 1, 1993

By Robert D. Rogers

The demand for phosphate will continue into the future, because phosphate is currently irreplaceable as a plant nutrient and in many chemical applications. Phosphate is not recycled, so the supply must be replenished through a process of mining and purification. Numerous microbial isolates. obtained from the environment were screened find those which demonstrated the greatest promise of solubilizing PO4 from the ore of interest. Screening was accomplished in a step wise manner an agar plate bioassay, shake flask studies, and semi continuous growth conditions. It was found that with the proper conditions of nutrient supply and solution pH; the bacteria and. fungus used in the semicontinuous process were able to solubilize in excess of 80% of an Idaho rock phosphate ore (RP) within nine days. A significant amount of solubilization occurred within the first six days. There was a 'reasonable correlation between the occurrence of soluble Ca and PO.4 during the processing of the RP thus providing evidence that the RP was being disintegrated by the organisms. In all cases, HPLC analysis of the solutions in which PO4 had been. extracted from RP showed that organic acids, which have been implicated as the mechanism of solubilization, were present.

Jan 1, 1991

By George P. Demopoulos

n this study we have sought to highlight the critical linkage between individual reaction kinetic parameters (usually determined in small bench scale experiments) and large continuous reactor performance by focusing on the industrially significant zinc pressure leach process. To this end a comprehensive mathematical model previously developed for the description of this process was employed. In this paper we have examined in particular how small variations in key kinetic parameters impact on the autoclave&apos;s performance, i.e. attainment of autogenous steady-state temperature, zinc conversion and solution chemistry. The reaction parameters studied were: (i) stoichiometry of the marmatite leaching reaction; (ii) the activation energy of the same reaction, E,; (iii) the rate constant of the ferrous to ferric oxidation reaction, k,; and (iv) the apparent equilibrium constant for ferric precipitation, K,. This parameter sensitivity analysis was done under no oxygen mass transfer control limitations. Model predictions were found to be more sensitive to the kinetic parameters under certain conditions than others. The most dramatic finding was the one related to the small amount of sulfate produced during marmatite leaching. In connection to this it was found that the small percentage (< 5 %) of sulfate produced enhances the autothermal operational stability of the autoclave. The need for accurate kinetic parameter determination under conditions similar to those encountered in industrial zinc pressure leaching was demonstrated.

Jan 1, 1999

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 Broggi Andrea

Condensates produced by SiO(g) and CO(g) have a crucial importance in silicon production. Condensation will follow the reactions 3 SiOðgÞ+COðgÞ→ 2 SiO2 + SiC and 2 SiO ðgÞ→Si+SiO2. Solid compounds generated during silicon production contain Si, SiO2 and SiC in different microstructures and amounts. In industrial systems, condensates limit the SiO(g) escape to the off-gas system. On the other hand, they can block the gas flowing from the high temperature zone, hence the necessity of studying an optimized condensation process. This review discusses SiO(g) condensation and its interaction with CO(g). The report gives an overview of the condensates found both at laboratory and at industrial scale. The two main compounds are the Si–SiO2 and the SiOx–SiC mixtures. The hypothesis on the mechanism of formation of SiC–SiOx condensates is presented through a wide selection of performed works. The advantages and disadvantages of the former experimental procedures are discussed.

By P. M. Swash

The paper describes the use of mineralogical methods in the exploration and evaluation of primary diamond occurrences. The most common methods that are used include the systematic search for kimberlitic indicator minerals, surface textural study of the indicator minerals, (garnet, spinel, ilmenite and chrome diopside) and alluvial macrodiamond studies so as to understand their provenance and guide exploration towards diamondiferous targets. The mineral chemistry of the indicator is used to positively assess the origin of the mineral grains and is also pivotal in the determination of the diamond potential of a deposit. Petrography of the primary deposit is able to identify the body to be kimberlitic and is also a support to the mineral chemistry findings. Unambiguous proof of a prospects potential to contain macrodiamond is proven by the occurrence of microdiamonds in the residues from the rock. The presence of a sufficient number of microdiamonds in the rock is enough to determine a semiquantitative grade estimate and warrant further metallurgical evaluation so as to determine its actual macrodiamond content.

Jan 1, 1991

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 I. Gaballah

Spent hydrorefining catalysts may contain 4 to 6 % of COO and/or NiO, 8 to 16 % of Moo3 and up to 10 % V205 generally supported by alumina. Raw samples are roasted in order to eliminate carbon, sulfur and hydrocarbons contained in the spent catalysts. The roasting optimum temperature and time are 500 "C and 7 hours. Selective chlorination of roasted samples with Cl2 + air, Cl2 + N2 and Cl2 + CO is investigated in order to recover the valuable metals. Depending on the chlorination it is possible to recover more than 80 % of the Ni and Co about 95 % of the Mo and up to 80 % of vanadium compounds. Cobalt and nickel chlorides are obtained by leaching the chlorination residues&apos; by acidified water. Molybdenum and vanadium chlorides and/or oxychlorides are obtained by selective condensation from the vapor phase. The chlorination of the catalyst support, Al2O3, can be limited to less than about 5 %. Besides the reaction temperature and time, the oxygen partial pressure of the chlorinating gas mixture appears to be the key factor for the reactions&apos; selectivity.

Jan 1, 1993