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By David K. Melgaard

Electroslag Remelting (ESR) is a complex process used to produce high quality specialty alloy materials. The quality can be directly correlated to variances in melt rate and immersion depth. Conventional ESR furnaces control these quantities using two independent control loops using proportional changes in current for melt rate and driving the electrode up and down to match a voltage set point for immersion depth. However it is well known that the control loops are highly coupled, i.e. changing the current to account for melt rate deviations changes the voltage depth relationship and vice verse. In addition the noise in measurements of the ESR process can be considerable, forcing conventional controllers to use highly damped responses. A new model-based controller has been developed to embody the coupling and improve responsiveness by using estimates from a reduced-order linear ESR model and the typical process measurements to control melt rate and immersion depth simultaneously. Kalman filtering is used to optimally combine the model estimates of eight process states and the measurements of voltage, current, position and mass to estimate the instantaneous melt rate and immersion depth. Several ESR melts under steady state and transient conditions were conducted to evaluate the performance of the new controller. This paper will discuss the design of the new ESR model and controller and will present experimental results demonstrating its much improved control and responsiveness. While this controller was developed for the ESR process, the effectiveness of model-based control in managing such a complex process with relatively simple equations suggests the approach could be employed for many other processes as well.

Jan 1, 2006

By T. M. Dreher

The difficulties associated with the operation of a classical rhodium refining process have prompted many attempts to develop a viable solvent extraction flowsheet for rhodium. Recent investigations at McGill University have involved the activation of rhodium prior to its solvent extraction. The role of activation is to convert the aquochloro complexes of rhodium to a form extractable by conventional solvent extraction reagents. In the novel separation scheme identified, chloro complexes of rhodium are converted to bromo complexes, which undergo aquation to a lesser extent, making them more easily extracted. Rhodium is then extracted using Kelex 100, and stripping is achieved by use of a concentrated chloride based solution. Separation of rhodium from iridium is achieved by either prior reduction of Ir(IV) to Ir(III), as the latter is not extracted, or via co-extraction and differential stripping. A conceptual flowsheet for the refining of rhodium using this method is proposed.

Jan 1, 1998

By A. Van den Steen

In the early fifties Professor Breckpot of the Louvain University in Belgium in collaboration with the Research Laboratory of Metallurgie Hoboken, discovered the possibility to separate nickel from cobalt sulfate solutions by a nickel sulfide depolarized cementation. This reaction, completed later with a zinc precipitation, was developed into purification processes for the Shituru and Luilu Gécamines cobalt plants in Zaíre. Due to increasing demand for higher quality products and the necessity of lowering the production costs, more laboratory and pilot plant investigations concerning the key parameters for the nickel and zinc sulfides precipitation were under- taken. Especially the relative stabilities of cobalt, nickel and zinc sulfides, precipitated with elemental sulfur or sodium hydrosulfide, were examined in relatlon with the pH and with the redox potential. These investigations have led to better plant practice and new development possibilities. The valorisation of the precipitated sulfides has also been considered.

Jan 1, 1988

By K. Pagalthivarthi, P. V. Desai

"During solidification of alloys, many inter-related physical processes, such as melt convection, mass diffusion, heat transport, macrosegregation and melt-undercooling occur. Several research workers have studied one or more of these effects separately. To answer important questions on solidification behavior, an overall approach interrelating the processes is necessaryAs a first step toward accomplishing the overall modeling, the freezing of a binary liquid metal is examined. The various stages during freezing of the alloy are critically described to build a continuum model for the entire process. Diffusive mixture theory is used to write the conservation equations for the liquid and the mushy zones. The concept of local thermodynamic equilibrium in the presence of curvature effects is used to restrict the number of degrees of freedom within the mushy zone. Constitutive equations relating flux quantities and affinities, the governing differential equations and boundary conditions are discussed briefly for the freezing process.IntroductionA solidification study encompasses such facets as solifidication time, microstructure, macrosegregation of the solute, shrinkage effects and soundness of the casting. Influence of one or more of the coupled heat and mass transfer phenomena such as local solute redistribution, thermosolutal convection, melt undercooling at dendrite tips and heat dissipation to the ambient have all been previously examined [1-3J. Several studies have examined the individual facets of alloy solidification as isolated processses. In fact, the transport processes occur simultaneously and a comprehensive model should include their inter-relationships. In particular, some of the existing studies of the mushy zone [4-6J do not emphasize thermodynamic completeness. This work represents an attempt to develop a thermodynamically consistent model of the entire solidification process on physical grounds."

Jan 1, 1986

By J. V. Atwood

The U.S. Bureau of Mines has developed a novel Double Membrane Electrolytic Cell (DMEC) that exhibits unique features for recycling contaminated metals and metal alloys. The DMEC incorporates two anionic ion exchange membranes, separating anodic and cathodic regions of the cell. The ion exchange membranes prevent significant transport of unwanted cationic impurities to the catholyte from the impure anolyte while the anion/cation balance in cell compartments is maintained through the free movement of anions between compartments. The membrane barrier makes it possible to electro refine highly contaminated materials or to electrowin from solution while utilizing alternate anode reactions. Sinceanolyte and catholyte cross contamination has been eliminated, premium cathode products are produced. The DMEC has been tested at bench, pilot, and commercial scales. Configuration of the DMEC, cell operation, scale, up efforts, and significant design factors are discussed. Two separate recycling investigations utilizing DMEC technology are presented. The first investigation examines recovery of high purity cobalt and nickel from severely contaminated super aIloy scrap. The second involves? upgrading contaminated cobalt in the U.S. Government's National Defense Stockpile. Capital and operating costs for both potential applications are presented.

Jan 1, 1995

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carned out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XQ >10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

Silver has the highest electrical conductivity of all metals and consequently this property is an attractive feature which makes it a leading candidate for use in electronic devices. The research conducted was focused primarily on the development of a process for obtaining a deposited silver-coating onto alumina, for applications related to electrical-conducting devices and, ancillarily, catalysts. Alumina balls and plane substrates were utilized for the investigation. The coating process employed an aqueous arnmoniacal silver-nitrate electrolytes with a formaldehyde solution as the reductant. Modifying additives - an activator which would be expected to promote good deposition-characteristics onto the (dielectric) substrate and an inhibitor which would obviate homogeneous reduction (precipitation) of silver was observed when the activator-containing silver-electrolyte reductant constituents were combined. However, the silver-electrolyte/reductant system with inhibitor could be employed (at 80°C) to achieve a viable (subject to future research optimization) coating on alumina. The influence of the processing temperature on the deposition process was delineated during the course of the research. The morphology of the deposited-silver on the alumina balls was assessed by SEM imaging. A tape-peel test was employed, with the plane substrates, to semi-quantitatively characterize the adhesion to the alumina.

Jan 1, 1998

By Matthew Jeffrey

Due to the increasing environmental and public concerns over cyanidation, there has been a large amount of research into viable alternative lixiviants. Despite these studies, there is little published data directly comparing the kinetics of gold leaching for each of these alternatives: most of the literature is concerned with gold extraction from ores. This paper presents a detailed kinetic study of gold leaching in cyanide, armmonia/thiosulfate and chloride/hypochlorite solutions. The gold leach rates were measured using a rotating electrochemical quartz crystal microbalance (REQCM). This instrument allows the mass of a gold sample to measured in?situ, with a sensitivity of less than 10 ng. From the results of these studies, it is possible to select experimental conditions where the leach rates of the alternative lixiviants are similar to that for the traditional cyanide system.

Jan 1, 1998

By Hee Dong Jang, Hong Yong Sohn, Miguel Olivas-Martinez

"Tetramethylorthosilicate (TMOS), a precursor of silica nanoparticles, is prepared from the waste silicon sludge, followed by the synthesis of silica nanoparticles from the TMOS by flame spray pyrolysis. A two-dimensional multiphase computational fluid dynamics (CFD) model for the flame spray pyrolysis process (FSP) for the synthesis of silica nanoparticles has been developed. The model incorporates the governing turbulent equations of overall continuity, momentum, energy and species mass transport to represent the gas phase and the population balance model (PBM) to account for the silica nanoparticles. The model has been validated with experimental data in terms of gas temperature and average particle size. Introduction Silica (SiO2) nanoparticles are used in various industrial applications, such as catalyst, pigments, thin film substrates, electronic and thermal insulators, and humidity sensors [1]. They are also used as additives in plastics and rubbers to improve the mechanical properties of elastomers, and in liquid systems to improve their suspension behavior. These applications rely on the particle morphology, average particle size, particle size distribution, and phase composition [2]. Silica nanoparticles can be synthesized by wet chemical processes such as sol-gel methods and high-temperature processes such as flame spray pyrolysis (FSP). The FSP process provides a unique control of particle size and crystalline structure and it can also produce high-purity, thermally stable particles continuously with minimal further treatments. The sizes of the flame- made particles range from a few to several hundred nanometers, depending on the operating conditions [1]. The synthesis of silica nanoparticles from organic compounds that contain silicon by the FSP process is of interest because it generates no harmful by-products [1, 3]. Several compounds such as tetraethylorthosilicate (TEOS) and tetramethylorthosilicate (TMOS) can be used to synthesize silica nanoparticles, but most such compounds are expensive. Thus, it is desirable to prepare the precursor compounds from waste materials. In the present study, TEOS and TMOS synthesized from silicon sludge were used as precursors of silica nanoparticles [4]."

Jan 1, 2008

By Hideaki Tokuyama

Recovery of Ni from acidic wastewater of metal surface treatment has been investigated for reuse of the metal and water. Ion exchange equilibria between Ni ion and a strong acid cation resin, DIAION SKIB, and effective diffusivity in resin particle have been studied and they related to the concentration of HCI. The amount of adsorbed Ni for unit quantity of resin decreases with the increase in HCI concentration. This trend is remarkable for acid concentration above 0.1 kmol/m3,. The exchanging ratio of Ni2+ to H+ in resin particle is I/2 and the values of equilibrium coefficient K and maximum exchange capacity Q are I.62 and 3.16 keq/m3 -dry resin, respectively. Effective diffusivity D. determined from the observed breakthrough curve increases with increasing concentration of DC!. A prototype of moving bed has been developed and applied for the recovery of Ni from model solutions of wastewater prepared by mixing HCl and NiCl2. This apparatus allows us to control the resin flow rate by changing the cross sectional area of hole I the Teflon plate installed at the bottom of resin bed. Characteristics of Ni recovery have been clarified under various liquid flow rates. In any case for Q1, Ni ion has been effectively recovered on SKIB resin and the removed fraction was more than 99.5 %. Higher loading ratio of ion is attained at larger liquid flow rate.

Jan 1, 2003

By Yousef Mohassab, Manoranjan Misra, Monalisa Panda, Eman Wahbah

This work studies the removal of arsenic (V), arsenate, and arsenic (III), arsenite, from aqueous solution using calcined Quintinite-3T. The two adsorbents Quintinite-3T was prepared, calcined at different temperatures, and characterized by XRD, BET, and SEM. The surface area of the calcined Quintinite-3T was 193.4 m2/g. The particles size ranged from 12 to 56 nm for the uncalcined Quintinite-3T and from 24 to 42 nm for the calcined Quintinite-3T. Kinetic analysis, adsorption isotherm, and factors affecting the adsorption were investigated. Calcined Quintinite- 3T retained As(v) and did not release it back to water even after an entire month.

Jan 1, 2016

By G. B. Harris

Jaguar Nickel Inc. is developing the Sechol Nickel-Cobalt Laterite Project in Guatemala, Central America. Recognizing the potential advantages offered by chloride brine chemistry, Jaguar, at the facilities of Process Research ORTECH Inc, Mississauga, has developed an Atmospheric Chloride Leaching Process using a mixed chloride lixiviant to recover the nickel and cobalt, whilst leaving the majority of the iron and magnesium in the leach residue. Subsequent solution purification and mixed nickel/cobalt hydroxide product recovery is by standard precipitation methods, using recycled caustic magnesia, with a final stage of pyrohydrolysis of a portion of the concentrated magnesium chloride brine for recycling both the caustic magnesia and chloride lixiviant. The flowsheet that has been developed also offers opportunities for by-product recovery and efficient, environmentally clean process effluent management. The paper discusses some of the early leaching results in the context of strong chloride brine chemistry, with emphasis on how the controlling of water activity, hydrogen ion activity and chloride concentration permits the selective leaching of nickel and cobalt from an iron-magnesium matrix. Keywords: nickel, cobalt, iron, magnesium, Sechol, Guatemala, chloride, pyrohydrolysis

Jan 1, 2004

By Jose R. Parga

In mining operations, cyanidation is the ,predominant method by which gold and silver are recovered from their ores and it is recognized that cyanide consumption can be a major factor that contributes to the operating costs for such operations. Also after extraction and recovery of precious metals a certain amount of cyanide is delivered to the tailings pond and must be considered with respect is environmental problems due to the toxicity of cyanides. In this regard, the Air-Sparged Hydrocyclone (ASH) has been used as a reactor for the treatment of cyanide solutions in two ways; first for cyanide recovery by acidulation using the Mexican modification of the Mills-Crowe process and second for cyanide destruction by oxidation with the use of chlorine dioxide (ClO2). In both cases, excellent performance can be achieved using the high capacity ASH system.

Jan 1, 1998

By R. Y. Wan

Low grade sulfidic-carbonaceous refractory ore from Newmont Gold Company's Carlin deposit was microbially pretreated. The biological pretreatment process gave partial oxidation of the sulfidic components of the refractory ore but the preg-robbing carbon continued to be active resulting in approximately zero cyanide gold extraction. A 495 ton pilot plant test heap was conducted using acidic thiourea leach following biooxidation. Activated carbon and cation exchange resin adsorption were tested for gold recovery from the thiourea pregnant solution. The results obtained from the test heap were not satisfactory. Gold extraction was low due to slow reaction kinetics which was caused by relatively large particles and very low winter temperatures. Problems existed in the thiourea-test heap and are discussed in this paper. An alternative heap leach process using thiosulfate has been successfUl at the pilot scale for gold extraction following biooxidation pretreatment of refractory sulfidic-carbonaceous ores.

Jan 1, 1995

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carried out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XO > 10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By Xiao Yang

Calcium oxide is one of the major fluxing agents used for steel refining. Because unreacted CaO remains in slag in most cases, discharged slag is difficult to be recycled smoothly. With the growth of environmental concerns, improving utilization efficiency of CaO is required to reduce the amount of discharged slag and energy consumption. The authors have reported a resource and energy-saving process by using multi-phase flux for dephosphorization. Reaction behavior of phosphorus in multi-phase CaO–FeOX–SiO2–P2O5 flux system was investigated. Formation mechanism of P2O5-rich phases was clarified at the interface between solid CaO or 2CaO, SiO2 and molten CaO–FeOx–SiO2–P2O5 slag. Phase relationship and thermodynamic properties of 2CaO, SiO2-3CaO, P2O5 solid solution were observed to confirm the condensation of P2O5 in solid phase. Based on these results, reduction of CaO consumption, discharged slag curtailment, and energy-saving effects in the novel refining process by using multi-phase flux were discussed.

By Larry G. Twidwell

The removal of dissolved arsenic from mine waste waters utilizing a lime/phosphate precipitation technique has been studied on a laboratory scale at Montana Tech of The University of Montana and on a pilot scale at MSE Technology Applications as a wastewater treatment process potentially capable of removing dissolved arsenic to <50 µg/L. Arsenic bearing lime and lime/phosphate slurries were subjected to laboratory extended-time air-sparged aging for over four years. The lime slurries released their arsenic back into solution in a relatively short period of time, whereas the lime/phosphate slurries showed limited release of arsenic. The developed process has been pilot scale tested by MSE-TA for the EPA Mine Waste Technology Program on three waters, ASARCO smelter blowdown water, ASARCO thickener overflow water, and Mineral Hill Mine groundwater. The laboratory study results will be presented and discussed in this presentation. The pilot scale results will be presented and discussed in a companion presentation. Stability, Aging, Apatite, Johnbaumite

Jan 1, 2005

By Eiichi Kuzuno, Atsushi Shibayama, Toyohisa Fujita, Kazuo Koike, Toshio Miyazaki, Hitoshi Masuda

"A solid sulfur is more useful to recover and store than a sulfuric acid as a by-product in the zinc hydrometallurgy. In this experiment a zin concentrate (sphalerite) was leached with ferric sulfate at about 373 K for 3 to 6 hours. Zinc was leached more than 95%. After a solid-liquid separation, the leached residue contained solid sulfur was obtained. The particles in the residue were dispersed by lignin and the solid sulfur of approximately 85% was recovered as float product by a flotation with frother in the pH 4. The dried float product was heated at 413K for 2 hours. The pure solid sulfur was recovered. On the other hand in the leached liquid a zinc oxide was ·added and ferrous .iron was oxidized to ferric iron by blowing oxygen. This ferric iron was returned to the zinc leached process after solid-liquid separation.IntroductionZinc concentrate is usually roasted as pretreatment in zinc hydrometallurgy and the produced S02 is changed to sulfuric acid. However, recently in Japan the utilization of sulfuric acid has been limited and it is more costly to store. Instead of producing sulfutic acid the solid sulfur recovery has been examined by direct leaching of zinc_ concentrate in this experiment.In the direct leaching, several kinds of effects have been studied for leaching of sphalerite in ferric sulfate solution. The addition of lignine siilfonate1 • 2) and fine· grinding3) increases the · speed arid leaching fraction of sphalerite. The leaching ratio depends on impurities in sphalerite ores4 • 5). Here, the zinc concentrate is leached ferric sulfate solution under atmospheric pressure at 373K. The solid sulfur in leached residue is separated as float products from other solids by sink-float separation and flotation. The sulfur in float products is purified by evaporation at 413K and recovered."

Jan 1, 2000

By Rina Kim

The addition of lead to a gold leaching reactor can effectively accelerate or retard the gold cyanidation reaction. This study explored the effect of lead on the gold dissolution kinetics using cyclic voltammetry (CV) experiments. It was illustrated that the gold leaching kinetics in the cyanide solution enhanced with the addition of lead salt in the low overpotential region (–0.35 V vs. Ag/AgCl). The similar behavior was observed in the presence of ore containing 0.25% galena. In contrast, the gold oxidation kinetics retarded at –0.35 V (vs. Ag/AgCl) in the presence of silicate and lead-bearing mineral under certain conditions. Likewise, the lead addition was not functional for the high sulfur ore. This was attributed to the oxidation of the sulfides to the elemental sulfur, which subsequently formed a passivating layer on the gold surface. The results were evidently affirmed by the electrochemical tests and X-ray photoelectron spectroscopy (XPS) analysis.

By Krzyszof Borowiec

With the aim of determining the thermodynamic conditions for sulfation of impurity elements, in particular magnesium, in titaniferous slags the equilibrium gas composition for the sulfation reaction: MO + so2 + 1/2 02 = MS04 has been studied by an EMF technique with a solid zro2 + Cao electrolyte. Here M denotes the impurity elements: Mg, Ca and Mn, and the following _oxide systems have been studied: Ti02-MgO-Fe2 o 3 , Ti02-MnO-Mn2 o 3 , and Ti02 -CaO-Si02 , all in the . temperature range 700-1000ºc. Reproducible EMF values were obtained by adding small amounts of -Na2so4 to the oxide-sulfate mixture. From the observed results the Gibbs energy of formation of the phases Mg 2Ti04 , MgTi03 , MgTi 2o 5 , MnTi03 , CaTi03 , and CaTiSio5 , as well as the activity of MgTi05 in the solid solution with Fe2Ti05 have been calculated. The results show that, from a thermodynamic viewpoint, sulfation of these impurities in titaniferous stags i:s favorable- at around and below 800ºC.

Jan 1, 1985