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By O. Forsén

A new cell construction was designed for the study of the electrochemical behaviour of additives in conditions that simulate real copper, electrorefining. The behaviour of gelatine and thiourea was studied by applying different electrochemical methods, i.e. polarization resistance and voltametric measurements. In this study, individual galvanostatic electrolysis experiments were carried out for 120 hours. The organic additives were introduced to the electrolyte at certain intervals and their concentration was varied in the range &om zero to four ppm. An optical microscope was applied for the examination of copper cathode deposit microstructures. The results show that gelatine has a polarizing effect on the deposition potential of copper whereas even small amounts of thiourea depolarize the electrodeposition of copper. The maximum inhibitor efficiency of gelatine was obtained at a gelatine concentration of slightly lower than two ppm. When both gelatine and thiourea were present in the electrolyte, the depolarizing effect of thiourea exceeded completely the polarizing effect of gelatine. If chloride ions were added to gelatine and thiourea containing electrolyte, the electrochemical behaviour of the system was altered drastically. Chloride ions resulted in the prevailing of polarization effect caused by gelatine while the depolarizing effect of thiourea disappeared in this system. The polarizing effect of gelatine increased until chloride ion concentration of 30 ppm was reached. Also, the above electrochemical phenomena could be detected in the optical examination of copper deposit microstructure.

Jan 1, 1995

By Kenneth N. Han

Thermodynamic and kinetic aspects of nickel and cobalt leaching from metals. minerals and ores in various media have been reviewed and discussed in this paper. A kinetic model developed to delineate the leaching mechanisms for these metals has been discussed in view of experimental observations. The current review also includes the dissolution behavior of nickel and cobalt from various minerals such as oxides, sulrides. ocean floor manganese nodules, and laterites. A particular emphasis has been extended to similarities and differences of the dissolution behavior of these two metals in various media. The leaching of nickel as well as cobalt metal in acidic solutions and arnmoniacal solutions exhibits in most part mass transfer controlling. although at some pH's, chemical controlling or mixed controlling mechanisms seem to prevail. The leaching of nickel and cobalt from oxides in acids and ammoniacal solutions. on the other hand, can be described best by chemical controlling mechanisms.

Jan 1, 1993

By J. Hamisch

Climate policy regarding perfluorocarbons (PFCs) may have a significant influence on investment decisions in the production of primary aluminum. This work demonstrates an integrated analysis of the effectiveness and likely economic consequences of different climate policy options. In our study we first compare atmospheric observations to the available estimates of PFC emissions for the baseline years 1990 and 1995. We then present projections for regional emissions of PFCs from the aluminum industry using the MIT Emissions Projection and Policy Analysis model under different policy scenarios. Abatement costs for emissions of PFCs and C02 are compared in the context of the Kyoto Protocol.

Jan 1, 1999

By T. T. Chen

A mineralogical study of copper anodes and copper anode slimes was carried out to elucidate the silver phases present and the behaviour of silver during copper electrorefining. Most of the silver in the anodes is in metastable solid solution in the copper metal. As the copper dissolves, silver also dissolves, but is rapidly removed from solution by a variety of reactions. Some of the silver is precipitated as Ag by cuprous ions and some is precipitated as a complex CU-Ag-Pb-As-Se oxidate phase. Much of the silver, however, reacts with copper selenides to form, progressively, (CU,Ag) 2se, AgCuSe and Ag2se. The reaction commences at the periphery of the selenide grains and progresses inward; the result is commonly a silver-rich species on the outside of a silver-deficient core. Slimes collected periodically throughout the electrorefining cycle show a progressive silver enrichment of the selenides. Traces of Ag2Te also may be present, but the telluride seems to J:ie a rare constituent of most raw anode slimes.

Jan 1, 1989

By M. L. Cunha

The lack of control of As and Sb compounds from copper smelters and converters has rendered some chalcopyrite containing arsenopyrite, stibnite and tetrahedrite minerals unusable for metal extraction. In the present investigation, we have studied the carbothennic reduction of Portuguese chalcopyrite mineral concentrate in the presence of lime/CaS04 and CaS04/Si02. Thermodynamic equilibrium calculations were performed to study the distribution of As and Sb between metal and the CaO-Si02-FeO slag phase. The phase equilibrium calculations also show the effect of oxygen partial pressure on the increase in the volume of the slag phase, which helps in lowering the copper metal formation temperature and facilitates a better separation between metal, matte and slag. The reduction reaction kinetics was studied between 850°C and 1100 °C, and the phases formed were identified by X-ray powder diffraction and scanning electron microscopy techniques. The importance of this research for using recycled matte, lean and rich minerals with As and Sb is also explained.

Jan 1, 2001

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 M. Nilmani, J. Sofra

The transverse distributions of the solids discharge velocity and mass flux at the discharge end of vertical and inclined lances were measured in order to detennine the transverse distributions of the axial momentum flux, which is a dominant factor influencing the penetration behaviour of particles into melts during submerged injection. The effects of gas velocity (10 - 30 m/s), solids loading (5 - 10), lance length (0.15 - 1.0 m), lance inclination (vertical downward - horizontal) and particle density (2500 - 8900 kg/m3 ) were investigated, while the lance diameter and particle size were fixed at 10 mm and 220 µm respectively. The particle velocities and mass fluxes were measured by image analysis of particles illuminated in a laser-generated light sheet aligned vertically through the axis of the lance at the discharge point. The particle discharge velocity profiles for vertical downward flows were synunetrical about the centre-line of the lance, with the maximum velocities occurring at the centre-line. The velocities increased with increasing gas velocity, increasing lance length and decreasing particle density in accordance with previous observations. The transverse mass flux profiles were also synunetrical for vertical downward flows, however at the lower gas velocities the peaks in the profiles were displaced from the centre-line of the lance by a fractional diameter of about 0.15. The particle discharge velocity profiles become increasingly asynunetric as the lance orientation was changed from vertical to horizontal, with higher particle velocities present near the top wall of the lance. The mass flux profile also became asyrrunetric as the horizontal orientation was approached, however in this case, the profile became biased towards the bottom of the lance. The effect was much more pronounced for a gas velocity of 10 m/s than for 30 m/s, showing the relatively stronger gravitational influence as the velocity was reduced.

Jan 1, 1996

By Youn-Bae Kang

Evaporation mechanism of S from liquid Fe–C–S alloys at 1873 K was proposed by analyzing available experimental data. It has been known that increasing C content in liquid alloy increases activity coefficient of S ðfSÞ, and it could raise driving force for the evaporation reaction S = S(g). However, experimental data of the evaporation of S in the Fe–C–S alloys could not be accounted for only by considering the increases of fS. In the present study, formation of carbosulfides, CS(g) and CS2(g), was additionally taken into account in order to explain role of C for the accelerated S evaporation. Surface adsorption of S was also taken into account, which retards the evaporation rate of S. An evaporation model equation was formulated. It can be applied to calculate the evaporation rate of S over wider C content (from zero to its saturation to liquid alloy).

The present work is mainly focused on developing intermetallic inert anodes for aluminum electrolysis. The anode alloy based on Al-Ti-Cu system was prepared by casting, followed by the application of a protective coating. Behaviour of corrosion and the passivation under anodic condition was characterized using the electrochemical and microscopic techniques. The results obtained clearly demonstrate that the oxide coating can provide good corrosion resistance via surface passivation of alloy anodes, rendering them inert in cryolite melt.

Jan 1, 2006

By Chai Li-yuan

Anodizing behaviors of magnesium alloys AZ31 at constant applied current, based on the electrolyte solution free of chromate or fluoride, were investigated. The anodizing process was influenced by constituents of electrolyte greatly. Therein, the oxylate salts, which led to the occurrence of the two totally different processes, played a determinant role in anodizing. They were stable and sparking process respectively. The morphology of anodizing film was observed by SEM and the structure of film was analyzed by XRD. During the stable process, a brown thin film was formed, however the sparking process led to the formation of white hard thick film. The functions of some kinds of additives, such as ammonia, glyceryl alcohol and PVP etc were also studied. Some of them had great effect on surface morphology of anodic film and some of them affected stability of anodizing process significantly.

Jan 1, 2006

By Chu Yong Cheng

Manganese is one of the main impurities in the recovery of base metals from their ores. This is especially true when laterite ores are processed using the pressure acid leach (PAL) process. The use of intermediate precipitation, solids/liquid separation and re-leach in the three Western Australian nickel laterite plants to separate nickel and cobalt from manganese and other impurities makes these processes complicated and costly in capital and operation. The research work carried out by the solvent extraction (SX) group at the A J Parker Cooperative Research Centre for Hydrometallurgy (CSIRO Minerals) has led to the development of direct solvent extraction processes to separate nickel and cobalt from manganese and other impurities. The simplicity of the process flowsheets and the expected savings in capital and operating costs are the major advantages of the new direct solvent extraction processes over the existing processes. By using a new synergistic organic system, Versatic 10 / dccyl-4-pyridinccarboxylatc ester, with a pilot plant leach solution from BHP¬Billiton (after iron precipitation), the metal values (Ni and Co) together with zinc and copper were separated from manganese and other major impurities (Mg, Ca and Cl) in the first SX circuit. The co-extracted manganese, magnesium and calcium were easily scrubbed out. The extraction and stripping kinetics of the metals with the new synergistic organic system were very fast and the synergistic system was found to be chemically stable. pH-extraction isotherms of metals with D2EHPA showed that the extraction order as a function of pH50 was Zn2+ > Ca2+ > Mn2+ > Cu2+ > Co2+> Ni2+> Mg2+. Semi-continuous test work with a cobalt pilot plant leach solution from Peko Rehabilitation Project Pty Ltd and a synthetic solution to simulate a concentrated laterite leach solution from BHP-Billiton showed that manganese, together with calcium, copper and zinc can be separated from nickel, cobalt and magnesium. This led to the development of another direct solvent extraction process to separate manganese and other impurities from nickel and cobalt and to recover nickel and cobalt from leach solutions. A project was initiated by HiTec Energy Ltd to recover manganese from waste laterite leach solutions using SX technology and to further purify it to produce high purity electrolytic manganese dioxide (EMD) for the high quality alkaline battery industry. Batch tests were conducted to select a suitable organic system for the extraction of manganese in terms of selectivity and extraction and stripping kinetics. A total of eight organic systems were tested using waste laterite processing solutions. A Versatie 10 / synergist system showed very promising results. By using the synergistic system, high manganese recovery would be obtained, fewer SX stages would be required and a higher A:O ratio could be used in extraction, resulting in a smaller organic inventory and lower capital costs. The risk of gypsum formation is also minimised with the synergistic system. Keywords: Solvent Extraction, Manganese, Laterite, Synergist

Jan 1, 2004

By O. Forsén

In the first part of this paper is studied the behaviour of small amounts of impurity elements? in the solidification of copper anodes. In the second part the dissolution of these impure anodes in sulphate based electrolysis is discussed. The first part is introduced with practical examples, the .model of solidification of impurities during the solidification of anode copper. According to this model the solidification structures of anode copper are strongly influenced by both thermodynamic and kinetic factors. Thermodynamics determine the microstructure of anode copper, but kinetics can alter the composition of melt to such that there is formed unequilibrium structures during the solidification, especially when the residual melt is solidified. The electrolysis experiments have clarified the behaviour of impuririties in the electrochemical dissolution in sulphate. Based copper electrolysis. In this study it is widely investigated to what extent any impurity elements or oxides will dissolve. In copper electrorefining. With the aid of the electrochemtcal experiments it was possible to fulfil quantitatively the qualitative results accomplished by microstructure studies.

Jan 1, 1985

By John Petersen

Heap bioleaching technology has become well established for the exploitation of copper sulfide ores. Still, in many operations the rate of copper extraction is rather slow, often taking two years or more to recover 80% of the copper. Chalcocite, the most common secondary copper sulfide, leaches by a two-stage mechanism. The first stage is rapid, whereas the second stage has a high activation energy and proceeds slowly at ambient temperatures. Nonetheless, this rate is still considerably faster than what is typically realized in a full-scale heap. A comprehensive column bioleaching study of a chalcocite ore has shown that the chalcocite columns are leached in a zone-wise fashion. The first zone corresponds to the first stage of chalcocite leaching, where all ferric produced by the bacteria is immediately consumed and all acid entering with the feed solution is consumed within a relatively narrow band. The second stage of chalcocite leaching proceeds much more slowly in the wake of the first stage, within a zone that grows gradually over the entire length of the column. The overall rate of leaching is thus determined by the rate of acid supply into the column rather than by mineral or bacterial kinetics, at least until the entire column is engaged in second-stage chalcocite leaching. In full scale heaps, there is evidence to suggest that solution distribution favours channelling between relatively large clusters of material which are exposed only to stagnant solution. Reagents have to migrate into such clusters by diffusion, which retards the delivery of acid dramatically. Thus, we believe that the rate of chalcocite oxidation in heaps is governed by sideways diffusion rather than downward migration. Column experimental results have been reproduced with a comprehensive heap-modelling tool. The model predicts that by simply changing the length of the average diffusion channel from column conditions (a few cm) to heap conditions (tens of cm), extraction times can change from weeks to years under otherwise identical conditions.

Jan 1, 2003

By Kurt A. M. Westerlund

The basic function of primary gas handling downstream non-ferrous pyro-metallurgical processes is cooling hot sticky gases to treatable temperature levels (e.g. entering ESP). That means managing efficient the critical gaseous components from a molten via a sticky to a solid phase. The article outlines the modem gas cooling methods combined with efficient heat recovery. Examples of the alternative use of recovered steam energy are outlined; as e.g. drying of concentrate and power generation. The heat transfer impact of the insulating dust is called fouling and circumstances causing fouling are described. Modem cooling surface design and cleaning techniques to keep fouling in reasonable limits are described. Leakage- and false air ingress into the gas handling lines often limits smelting capacity. The objective is generally to minimize the infiltration of air but it still takes place at open interfaces (e.g. at reactor hood, feed port). Leakage air at furnace roofs for example can be reduced to a minimum by adopting the pressure gas sealing used at present In-Bath-Lance furnaces. Modernization and optimization methods to de-bottleneck existing waste heat boiler gas cooling capacity by highly efficient surface cleaning systems and false air avoiding (e.g. bundle roof boxes, dust discharge) are detailed described.

Jan 1, 1999

By Vinod K. Sikka, René Cooper

"Cohoes, New York 12047 Intermetallics are an attractive class of advanced materials. The aluminide intermetallics offer advantages including: (1) lower density, (2) oxidation resistance, (3) carburization resistance, and (4) interesting mechanical properties because of their ordered crystal structure. Even though the attractive properties of the aluminides and other intermetallics have been known for nearly four decades, their practical applications have not been developed for two reasons: (1) the poor ductility (in some cases, both ambient and high temperatures) and (2) the lack of processability into meaningful components. Recent advances such as ductilization of Ni3Al by small additions of boron and the knowledge that environmental effects are the major cause of poor ductility in Fe3Al and FeAl systems have brought the intelmetallics into the forefront of research and their commercial applications. This paper has described a method for melting Ni3AI-based alloys that successfully utilize the exotherrn for the formation of NiAl from the elemental materials. The reaction-synthesis method has also been utilized for the production of NiAI and NiAI-based alloy powders from the elemental powders. The reaction-synthesized powders of NiAI and NiAI-based alloys were consolidated by hot extrusion and evaluated for tensile properties over a temperature range from room temperature to 1050ºC. The powder-processing conditions have been found to have more influence on the ductile-to-brittle transition temperature of NiAI than the powder-production method.IntroductionIntermetallics are an attractive class of advanced materials [1-11]. The alum in ide interrnetallics offer advantages including: (1) lower density, (2) oxidation resistance, (3) carburization resistance, and (4) interesting mechanical properties because of their ordered crystal structure. Even though the attractive properties of the aluminides and other interrnetallics have been known for nearly four decades, their practical applications have not been developed for two reasons: (I) the poor ductility (in some cases, both ambient and high temperatures) and (2) the lack of processability into meaningful components. Recent advances such as ductilization of Ni3Al by small additions of boron and the knowledge that environmental effects are the major cause of poor ductility in Fe3Al and FeAl systems have brought the intermetallics into the forefront of research and their commercial applications. The paper will briefly review the processing techniques being pursued for the commercial applications of Ni3Al-based intermetallics. The major emphasis of the paper will deal with synthesis of Ni3Al and NiAI intelmetallics."

Jan 1, 1994

By C. A. Young

The remediation of cyanide (CN-) and nitrate (NO)-) anions in mine and agricultural waters by various photolytic methods has been reviewed and investigated. Photolytic methods such as direct photolysis, homogenous photolysis, and heterogeneous photocatalysis are briefly described and compared. Results and discussions show that each method has certain advantages and disadvantages. For each method, Eh-pH diagrams prove useful for determining reaction mechanisms. Preliminary results obtained for cyanide oxidation and nitrate reduction show that homogeneous photolysis can be superior due to faster kinetics than the other methods. The photolytic methods were individually, not simultaneously, tested and compared. Differences in concentrations of products were obtained and attributed to differences in photoconversion efficiencies and other inherent characteristics of .the photolytic methods. Various reaction mechanisms are proposed in accordance with the literature as well as measurements obtained from solution analysis using ion selective electrodes and ion chromatography .

Jan 1, 1995

By F. Garcia-Carcedo

This research aimed to develop a clean technology for the production of ZnO from residues generated by the steel making industry. Scientific and technologic parameters were both investigated in order to define an industrial methodology allowing the integral recycling of EAF dusts. A reengineering of the Waelz process was perform,~d, aiming to produce a clean fraction of ZnO, fluorine free, as well as a slag enriched in metallic iron, which can be recycled in electric arc furnaces. The technical conditions used to produce the ultra pure fraction of ZnO are described. The magnetic separation of the EAF dust allowing the production of a phase high in iron and recyclable to the electric arc furnace is also discussed. Thermodynamic of the volatilization of all the elements contained in the EAF dust was performed in order to better control the thermal process in the rotary kiln. Tests were run using different reducing agents, weakly or highly reactive, aiming to determine their specific efficiency.

Jan 1, 2000

By Xiang Ma, Halvor Dalaker, Kai Tang, Stefan Andersson

Silicon carbide (SiC) is one of the most important non-oxide ceramic materials for many industrial applications and is mainly synthesized by carbothermic reduction of silicon oxide by coke above 2200°C. Replacing natural gas (mostly methane, CH4) for coke in SiC synthesis could considerably reduce energy consumption and CO2-emissions owing to higher carbon activity of CH4 at lower temperature. The generally accepted reaction mechanism is that SiC is synthesized through gaseous intermediate silicon monoxide, SiO. In the present study, the reaction mechanism for the SiO and CH4 gaseous mixture has been examined using atomic scale modelling. Molecular dynamics (MD) using a reactive force field (ReaxFF) has been utilized to examine the initial stages of reactions involving a gas mixture of SiO and CH4 and surfaces of SiC. The MD results revealed some interesting SiC formation mechanisms. The reaction energies of the critical intermediate species were also estimated by density functional theory (DFT) calculations and the implications for the force field parameters used in ReaxFF was discussed.

Jan 1, 2015

By Y. A. Chang, L. M. Pike, C. R. Kao

"Knowledge of the site preference of ternary solute additions is essential to developing an understanding of how these solutes affect the properties of B2 intermetallic compounds. A quasichemical model will be presented which is able to predict the site preferences of dilute solute additions to tliple defect B2 compounds. The only parameters required are enthalpies of formation at the stoichiometric composition. General equations are developed which can be used to determine site occupations and defect concentrations for dilute as well as non-dilute solute additions. These equations use atom pair bond enthalpies as the parameters. It is found that the site preferences of dilute additions are not always in agreement with predictions based on the solubility lobes in ternary Gibbs isothelms. Predictions for dilute additions to NiAl and FeAl are compared to expel1mental results found in the literature. Satisfactory correlation is found between the model and the experimental results. In addition, the predictions from the model on vacancy concentrations in Fe doped NiAl are compared to recent experimental results by the authors.1.0 IntroductionIntennetallic compounds with the B2 crystal structure such as NiAl and FeAl have been investigated recently for possible use as structural materials in high temperature, oxidizing, and/or corrosive environments. The major limiting property of these materials has been a lack of sufficient room temperature ductility. Attempts to improve the ductility have often been made through ternary or higher order alloying. For B2 compounds, substitutional alloying additions can occupy either of the two sublattices and this site occupancy can be crucial in determining how the alloying addition affects the properties of the alloy. In this manuscript we will discuss the use of thelmodynamic modeling to predict the site occupancies of ternary alloying additions in B2 compounds with the triple defect structure."

Jan 1, 1996

By Laurent Cohen

Since the 1970s, Solvent Extraction (SX) in hydrometallurgical processes has been a key enabling technology in the production of high-purity metals. Examples include copper, rare earth oxides, uranium, cobalt and nickel. Notwithstanding incremental improvements in extractant formulations, few breakthroughs can be recounted in this industry outside of the initial amine-, oxime- or phosphine-based reagent chemistries. However, the advent of lithium-ion batteries and their stringent requirements for critical materials (lithium, cobalt and nickel) offer new challenges and opportunities for SX. Solvay recently introduced a new extractant for lithium, CYANEX® 936, and developed unique modeling software capabilities in cobalt/nickel separation using CYANEX® 272, zinc SX using DEHPA® and rare earth separations using CYANEX® 572. This paper discusses trends in SX and provides insight on processing of critical materials essential to energy sources. It also summarizes the technical and economic benefits based on extractant selection and advances in modeling.