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By N. Bazzanella

The hydrogen desorption kinetics of pure and Nb-doped magnesium hydride film samples was investigated by using a Sievert-type apparatus. The overall activation energy and the reaction order controlling desorption are (141±5) kJ mol-1H and n 4 for Mg hydride and (51±5) kJ mol-1H and n 1 for Nb-doped (5% at) Mg hydride indicating that, in the doped sample, hydrogen desorption is controlled by the H migration in transformed h-Mg layers. Structural analysis performed by X-Ray Diffraction (XRD) and Extended X-Ray Absorption Fine Structure spectroscopy (EXAFS) show that the catalytic effect of the Nb dopant is connected with the formation of NbH0.89 nanoclusters dispersed in the Mg hydride matrix. It is suggested that the catalysis process is also connected to the presence of Mg-Nb hydride interfaces where the transfer of H atoms preferentially occurs by connecting h-Mg grains and by the role of the MgH2-NbH0.89 interface as preferential site for the dissociation of the hydride phase.

Jan 1, 2006

By Lauri Holappa

Copper converting is mostly performed in Peirce-Smith converters. The process is still very similar to the original one developed in the early 20th century. It is a batch process in a horizontal cylindrical reactor with air blowing via tuyeres along the length of the reactor side. The Peirce-Smith converter has its roots in Bessemer's inventions in the 1850's as he tested both horizontal and vertical vessels for steel converting. However, for steel making a vertical pear-shaped converter with air bottom-blowing was established. In the course of time, there was a distinct necessity for oxygen usage instead of air due to harmful effects of nitrogen to steel properties and its cooling effect. In-bath blowing of oxygen did not succeed, however, and top-blown oxygen converter with oxygen lance (LD or BOF) was first developed in he 1950's and emerged rapidly to a dominating position. Somewhat later oxygen bottom-blowing via special shrouded tuyeres was developed (OBM or Q-BOP) but has attained only fractional share. Bottom-blowing technique had, however, impact on the current combined blown converters which adopted the benefits of both top and bottom blowing. In copper converting Peirce-Smith type converters have kept their position until today although new processes have been introduced and at least few of them seem to be emerging. In one respect copper converting has a clear leading position i.e. in the progress of continuous converting processes (Mitsubishi, Ausmelt). These processes utilise top-blowing lances instead of in-bath blowing tuyeres. A different principle for continuous converting is flash converting by Kennecott Outokumpu, which makes smelting and converting independent of each others. Solid ground matte is used as a feed for flash converting in a reactor shaft similar to Outokumpu matte flash smelting. A comparable process has been presented by Inco too. The paper discusses principal physico-chemical and process technical similarities and differences in copper and steel converting. Although these processes are metallurgically quite different it seems that during the modem history of ferrous and non-ferrous metallurgy, starting from the 1850's, the exchange of knowledge between these disciplines has been quite intensive. In long-term perspective, many similarities in the development can be found but also divergences due to different ambient circumstances.

Jan 1, 2003

By Hector M. Henao

To provide thermodynamic data for converting nickel matte to liquid nickel at high temperature, an experimental study was conducted on the phase equilibrium between the Ni-S alloy and the FeOX-SiO2, FeOx-CaO, and CaO-A12O3 base slag in a magnesia crucible and the CaO-Al2O3-MgO slag in an alumina crucible. All experiments were carried out at 1773 K under controlled pso2 of 0.1 atm and po2 in a range between 5x10- and 10-5 atm by using CO-CO2-SO2 gas mixtures. The dissolution of nickel in the slag was found to be minimum for the CaO-Al203¬-MgO slag with a molar ratio of NCaO/NA1203=1.7. The solubility of nickel in this slag at p02 of 6x10 atm (just before the precipitation of solid NiO) was 4 mass%. This result suggests that a CaO-A12O3 base slag could be used in converting Ni-S melt to nickel while minimizing nickel losses to the slag.

Jan 1, 2002

By Shun Myung Shin, Dong Hyo Yang

Cobalt is recovered from square type of spent lithium ion batteries (LIBs) containing 5~20 % Co, 5~7 % Li, 5~10 % Ni, 15% organic chemicals, and 7% plastics together with Cu, Al, Fe, and Mn. The waste LIB was prepared by physical treatment. After screening, the crushed LIBs were separated to +8 mesh, -8/+16 mesh, and -16 mesh powder. Among these, -16 mesh powder was selected for leaching. The leaching test was investigated at 2 M H2SO4, 6 vol.% H2O2, reaction temperature 60 ?, agitation speed 300 rpm, solid/liquid ratio 50 g/ 500 ml, reaction time 1 h. The leaching efficiency of cobalt was more than 99 % and its concentration was 24.9 g/L. For removing of impurities such as copper, iron, and aluminum in the leaching solution before cobalt solvent extraction, the impurities were eliminated by pH control with alkali solution. For selective extraction of cobalt, the aqueous phase removed impurities was equilibrated with different volumes of 0.4 M Cyanex 272 saponified of 50 %. Extraction efficiency of cobalt was about 80 % at first step. Separation coefficient (ßCo/Li) of cobalt and lithium extractions was 206.5. Over 9.0 % of pure cobalt sulfate solution was obtained after stripping with H2SO4 solution.

Jan 1, 2008

By Ryosuke O. Suzuki

A combined process of electrolysis of CaO in the molten CaCl2 and of calciothermic reduction, so-called OS process, was applied to prepare metallic vanadium directly from V2O3. The fine metallic powder containing 1860 mass ppm oxygen was obtained using 0.5mol%CaO-CaCl2 melt for 10.8 ks at 1173 K. The oxygen level did not decrease further even when twice electricity was applied. Because the metallic vanadium could be electrochemically deoxidized to the level of 10 ppm oxygen from 1.48 %, the large amount of by-product, CaO, due to reduction and the large surface area of the fine particles are the reasons of high oxygen content in the reduced powder.

Jan 1, 2006

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 Edgar Peek

Lixiviant regeneration is by definition a precondition for any hydrometallurgical process. In chloride hydrometallurgy either HCl or Cl2 has to be regenerated in order to establish an economically viable metallurgical process. One such regeneration process is widely used with steel pickling where HC1 is regenerated through the thermal decomposition of ferrous chloride in either spray roasters or fluid bed pyrohydrolyzers. This standard HC1 regeneration process deserves to be considered as a potential separation process, since thermodynamic calculations show that a fluid bed pyrohydrolyzer can function as a ferrous-nonferrous separator. Several nonferrous,metals such as zinc, lead and cadmium can be volatilized as a chloride under ferrous chloride pyrohydrolysis conditions. If such a nonferrous metal volatilization could be achieved in the case of slurry feeding of "contaminated" iron oxides, then this would increase the Fe/H2O ratio of the (process) feed and thus save on fuel per ton of iron, while yielding a marketable iron oxide product. Previous test work on synthetic materials revealed that the near-complete separation of zinc, lead and cadmium from iron oxide was possible in a pyrohydrolytic atmosphere, even if zinc was present as zinc ferrite (more than 99.5%). This investigation, which was carried out in a tube furnace at 1100 K has now been extended to treat synthetic zinc minerals and also franklinite ore. For the latter, it was found that 85% zinc volatilization could be achieved in 4 hours at 1300 K. It is postulated that complete zinc volatilization could not be attained due to the formation and/or presence of gahnite and hardystonite, which might be stable in HCl/H2O atmospheres at 1100 K. The effect of adding small amounts of calcium chloride to react with gahnite and hardystonite to give zinc chloride and both calcium aluminates and silicates is being discussed. Test work on slurry feeding of this complex ore in a recently constructed 4-inch diameter fluid bed pilot unit has been planned for the near future.

Jan 1, 1995

By Andreas Siegmund

Cast or rolled lead anodes employed in zinc electrowinning typically contain between 0.5?1.0% silver to decrease the overall corrosion rate. The production of cast lead-silver or lead-silver-calcium anodes often results in the formation of numerous holes, voids or laps in the anode surface that can initiate internal corrosion in localized areas. In rolled anodes the presence of internal porosity is significantly reduced, thus resulting in extended service life. The obtained grain structure of cast or rolled Pb-Ag anodes, however, requires a relatively long period of time to form a stable protective PbO2/MnO2 layer that can evolve oxygen without excessive lead contamination of the cathode. Therefore, these anodes are often mechanically, chemically or electrochemically conditioned prior to being placed in the electrowinning process. RSR Technologies has developed an improved anode for zinc electrowinning. The anode consists of a rolled Pb-Ag-Ca-alloy with controlled surface grain structure. The preferred calcium and silver content of the alloy is 0.05?0.08 % and 0.3?0.4%, respectively. Since May 2001, industrial-scale tests have been carried out at two zinc refineries in North America in industrial electrowinning cells. The controlled grain structure of these anodes allows forming an adherent protective oxide coating within a short period of several days when placed in an electrowinning cell without the necessity of being preconditioned. Anode sludge growth is evenly distributed. The anodes stay dimensionally stable and no short-circuits have been observed. Consequently, low corrosion rates and improved current efficiencies have been achieved.

Jan 1, 2003

By Sheng-hai Yang

The ultrafine, monodispersed, spherical cobalt powder has been fabricated by reducing cobalt hydroxide with glycol. It were investigated that the effect of NaOH concentration on the reaction rate and the effects of the concentration of cobalt hydroxide and surfactant on the morphology and particle size. The particles were characterized by the X-ray diffraction(XRD), scanning electron microscope(SEM), laser diffraction particle size analyzer and BET specific surface analyzer respectively. The XRD shows that the cobalt powders exist mostly in face centered cubic (fcc) structure, a little in simple hexagonal. The cobalt powders prepared at Co(OH)2150g/L, NaOH 40 g/L and surfactant 30g/L, its average particle size, specific surface area and cobalt content, were 0.88µm, 2.705m2/g. and more than 99.5% respectively.

Jan 1, 2006

By O. Barbosa F.

The thermochemistry of the systems SCN-H2O, Au-SCN-H2O and Ag-SCN-H2O is discussed. Potential-pH diagrams at 25°C are drawn for each system considering several sets of concentrations of the species involved. The information provided by the potential-pH diagrams is.complemented by distribution curves for each series of gold and silver complexes with thiocyanate. The analysis includes comparisons between the thiocyanate systems and the analogous cyanide systems, pointing out analogies and differences between the leaching of gold and silver with thiocyanate and with cyanide. The possibility of using soluble oxidizing agents such as ferric ions, hydrogen peroxide and Caro's acid is evaluated. The thermodynamic data used in the calculations and the chemical reactions represented in the Pourbaix diagrams are all reported in three Appendices. The overall results indicate the thermodynamic conditions for gold and silver leaching by thiocyanate.

Jan 1, 1989

By R. Cheng

The kinetics of the solvent extraction of ythium from HCl solution with mono-2-ethyl hexyl phosphonic acid mono-2-ethyl hexyl ester (HEHEHP) have been studied using a rotating diffusion cell (RDC). The effects of rotation speed, pH, ymium and extractant concentrations and temperature on the rate of extraction were examined. The rate of extraction of ythium appears to be controlled by an interfacial reaction of metal ion and extractant. The concentration of the latter is determined mainly by diffusion through the membrane. The contributions of the rates of diffusion in the diffusion layer, diffusion in the membrane and chemical reaction at the interface to the overall rate have been calculated on the basis of a kinetic model.

Jan 1, 1992

By Thomas P. Battle

Ilmenite (iron titanate) is the source of over 90% of all the titanium produced in the world today. At some point during production of titanium dioxide or titanium metal the iron impurity must be removed. Too often it becomes a waste instead of a product. DuPont and MINPRO have developed a solid-state process which separates the iron and titanium components of ilmenite into different high-purity powders, which can be separated using conventional mineral processing techniques. The main reactor in this process is a unique high-temperature ball mill, where the iron segregates from the ilmenite lattice with the assistance of catalytic quantities of He\. The results of lab, pilot plant, theoretical, and scale-up studies are presented and discussed.

Jan 1, 1996

By G. S. Rao

Levitated drops of Fe-18%Cr-2%C were reacted with oxygen-argon mixtures to study the reactions that occur in the AOD process, where the gases are injected into the melt and form bubbles. In the laboratory an argon-oxygen pulse, followed by pure argon, was flowed past the levitated drop to simulate the transient conditions in the gas phase as the bubbles rise in the melt. Oxide layers formed on the drops immediately when they came into contact with gas pulses containing 75% or more oxygen. Once the oxygen flow had ceased, the oxides reacted with the carbon in the drops to form CO gas and eventually disappeared. The de-carburization reaction occurred without oxide formation when the gas contained 50% oxygen or less. Melts that were sampled after EAF tapping, ready to be charged into the AOD, showed a higher tendency to oxide formation and consequent carbon boil than pure ternary Fe-18%Cr-2%C alloys made in the laboratory. The actual steel samples contained significant impurities, such as 0.25% Si and 0.56% Mn. A similar effect of oxide-forming impurities had been observed previously with binary Fe-C alloys. Movies were taken of the oxide formation and decomposition, and the results will be presented, along with data on the experimental conditions, including temperature and oxide compositions. The results are important because they give an insight into the reaction mechanisms in the AOD, which must be understood in order to improve and model the process.

Jan 1, 2006

By T. T. Chen

Hydrometallurgical products are difficult to characterize because of their fine grain sizes, heterogeneity, often amorphous structures and water soluble or hydrated constituents. Such products are advantageously studied using complementary mineralogical techniques including >50, ore microscopy, SEM-EDX, electron microprobe analysis, selective leaching and wet chemical analysis to determine the phases and their morphologies, to identify specific element carriers, and to elucidate the chemical reactions occurring during the metallurgical process. Sample preparation is an important consideration for these materials. For extremely fine-grained particles, or soft and brittle products such as elemental sulphur, the study of loose powder mounts provides information not available from the examination of polished sections. To demonstrate the application of the various mineralogical techniques, commercial zinc roaster calcines and leach residues, copper refinery anodes and anode slimes, and laboratory bornite leach residues were examined in detail. The various sample preparation and mineralogical methods are presented, and the use of these complementary and practical mineralogical techniques to improve the understanding of a particular hydrometallurgical system is discussed.

Jan 1, 1989

By Akira Yazawa

Oxidic dissolution loss of metal in slag is discussed thermodynamically in terms of oxygen potential, activity coefficient and equilibrium constant. To understand basic principle, regular solution model is applied for model calculation of the activity behaviour of metal oxide in FeO-SiO2-CaO slag, and effects of slag composition, temperature, and basicity of oxide on dissolution loss are demonstrated. As: a simplified but practical conclusion, the dissolved metal loss in slag is inversely proportional to activity coefficient of metal oxide, and also to FeO content in slag when amount of slag is taken account.

Jan 1, 1994

By C. A. Silva

Ladle change-over, during continuous casting of steel, initiates transient flow in the tundish which influences the inclusion content and degree of mixing between two consecutive batches of steel. The mixing behavior in the tundish during this period is determined by the casting rate and the ratios of: inflow to outflow during the refilling period; and, the low liquid level relative to the nominal level in the tundish during the transiency. A 3:10 scale water-model of a typical one strand slab caster was operated in conjunction with a tracer technique to characterize the velocity fields for several combinations of these parameters. Steady operation, a limiting case of the transiency, provided a basis for comparison. High-order moments -- skewness and kurtosis -- of the residence time density function have been utilized as signature elements associated with a particular residence-time distribution for the system. A simple mathematical model incorporating the above parameters as well as a characteristic Peclet Number was successful in simulating the features of the transient period.

Jan 1, 1993

By G. G. Barbante

Copper anode slimes are a valuable source of the precious metals, and selenium and tellurium. They are mineralogically complex and this has led to a great variety of process flowsheets for treating them. The traditional pyrometallurgical method utilises oxidation in a reverberatory furnace, but has numerous shortcomings. Recently deep-bath intensive smelting methods have been developed for use in the larger refineries. Despite these process advances, the thermodynamics of the reactions involved remains poorly understood. An initial description of the thermodynamics of slimes smelting is presented, but is severely limited by a lack of basic data. It is shown that slimes smelting is superficially similar to copper converting, but has many unique features. More basic thermodynamic data on selenium-based systems are needed before the process model presented can be further refined, and work in this direction has already commenced.

Jan 1, 1994

By Sung-Mo Jung

Experiments were carried out on a system with artificially prepared slags in a graphite crucible, in order to examine the possibility of recycling BOF slags produced in the steelmaking process. More than 80% of FeO and P2O5 was reduced within 20 minutes and the FeO reduction rate was greater than that of P2O5. P2O5 reduction began after more than 60% of FeO was reduced. Increasing slag basicity enhanced the reduction of FeO and P2O5. Temperature also improved slag reduction. The overall reduction rate was controlled by the chemical reaction at the slag/carbon interface. The reduction rates of FeO and P2O5 were second and first order with respect to their respective contents. Most of the reduced phosphorous is believed to vaporize in the form of P2 gas.

Jan 1, 2006

By B. Farouk, D. Apelian

"A numerical model has been developed to predict the temperature history of particles injected in a low pressure d.c. plasma jet. The temperature and velocity fields of the plasma jet are predicted as a free jet by solving the parabolized compressible Navier-Stokes equations using a spatial marching scheme. Particle trojectories and heat transfer characteristics are calculated using the predicted plasma jet temperature and velocity fields. Correction factors have been introduced to take into account non-continuum effects encountered in the low pressure environment. The plasma jet profiles as well as the particle/plasma interactions under different jet pressure ratios (from underexpanded to overexpanded) have been investigated.I. IntroductionIn the plasma spraying process a d.c. plasma jet is used as a heat source to melt and accelerate powder particles which subsequently impinge and solidify on a given substrate. During low pressure plasma deposition (LPPD) prooess, the plasma jet is expanded into a low pressure environment (40-80 Corr) which results in high plasma jet velocities with Mach numbers ranging from 2 to 3. Previous efforts to predict heat transfer and fluid flow in plasmas have made use of incompressible flow formulation employing turbulence models [1-3] for atmospheric plasma spraying. However, these theoretical calculations have been limited to the subsonic flow regime; hence, the compressibility effects and viscous heat dissipation were neglected. In the LPPD process, the plasma jet is operated at the supersonic flow regime, therefore, the compressibility effects and viscous heat dissipation are no longer negligible. This is the main motivation of this work.In addition, production of high quality dense deposits requires that a large fraction of the injected particles be in a molten state when they impact the substrate. An additional motivation for this work is that it is important to understand the plasma/particle heat and momentum transfer since these phenomena dictate both the particle thermal history and particle trajectory.Early computational works in supersonic nozzle field flow [4,5,6] consisted of patching methods that divided the flow field into an invisoid free stream and a viscous boundary and. mixing layers. Each was analyzed independently and coupled through appropriate boundary conditions. Later schemes [7,8] involved solving time-dependent, compressible Navier-Stokes equations over the entire computational domain. These schemes show a great promise in predicting flows with complex structure, and where the viscous effects became prevalent."

Jan 1, 1986

By M. D. Crites

As part of a multi-year program for assessing the viability of chrome-free refractories in copper smelting, converting and refining furnaces, dynamic corrosion tests have been conducted on a series of refractories from the magnesia-alumina system, using a ferrous silicate slag. The corrosion rates of the test refractories are compared with those of a reference mag-chrome brick, and recommendations are made for more in-depth evaluations of the more corrosion-resistant materials.

Jan 1, 1999