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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 Masatoshi Ogasawara

Saganoseki smelter & refinery operated two flash smelting furnaces, producing a combined 330,000 metric tons per year (hereinafter mtpy) of copper. [n 1996, however, it successfully shifted to a single fumace operation while maintaining production at the same level. Since then, the production capacity has been further increased to the present 470,000 mtpy by technological improvements. Also, in order to reduce the converter load which represents a bottleneck in efforts to increase production, the matte grade was gradually increased and currently runs at 65 to 66% attaining the low copper content in the slag (hereinafter slag loss) of 0.7 to 0.8%. This ' paper introduces some improvements, recent operation results and thermodynamic analyses.

Jan 1, 2003

By Takahiro Miki

In order to use metallurgical grade silicon (MG-Si) as a starting material for solar cell, phosphorus has to be removed from silicon because phosphorus is a n-type dopant. On the other hand, silicon, ferrosilicon, and silicomanganese are widely used as deoxidizers in steel refining processes. Since most of the phosphorus introduced during the deoxidation process is brought into final products, it is important -to lower the phosphorus content of these alloys. Hence, thermodynamics of phosphorus in such metals is important for the evaluation of dephosphorization processes. In the present study, thermodynamic properties of phosphorus in molten Si-P alloys at 1723- 1848K and those of Si-Fe-P and Si-Mn-P alloys at 1723K have been determined by equilibrating respective metals in a controlled phosphorus partial pressure. The results are expressed as follows.

Jan 1, 1998

By George S. Dulikravich

An advanced semi-stochastic algorithm for constrained multi-objective optimization has been adapted and combined with experimental testing and verification to determine optimum concentrations of alloying elements in heat-resistant and corrosion-resistant H-Series austenitic stainless steel alloys. The objective was to simultaneously maximize a number of alloy's mechanical properties. This research will result in a rigorous tool for the design of high-strength H-Series steels and other types of alloys unattainable by any means existing at the present time. Such a material-by-design tool will also be able to reduce or minimize the need for the addition of expensive elements such as Cr, Ni, Co, Nb, Ti, V, etc. and still obtain the optimum properties of an alloy.

Jan 1, 2003

By Aiyuan Ma, Tu Hu, Chenyu Sun, Yonggang Zuo, Hongying Xia, Jinhui Peng, Libo Zhang, Yongguang Luo

"In this study, the adsorption characteristics of tannin acid in aqueous solution were investigated using regenerated activated carbon (AC), with the aim to remove the tannin acid organic matter from the solution after zinc hydrometallurgy and Ge precipitation. Results showed the temperature has little effect on the adsorption ability (q.) of the regenerated activated carbon. The experimental equilibrium data were tested for the Langmuir and Freundlich isotherms. The adsorption equilibrium was better described by the Langmuir isotherm (R2 > 0.99). Pseudo first- and second-order kinetic models were used for describing kinetic data. It was determined that the kinetics of tannin acid removal was well fitted by second-order reaction.IntroductionGermanium recovery is a complex processes [1]. Hydrometallurgical processes are favoured and these are based on the precipitation of germanium as hydroxide or sulphide or alternately with tannic acid [2]. However, in the germanium recovery process, too much tannin is consumed by the germanium-tannins complexation process, and results in a high content of tannic acid remaining in solution, which is harmful to the valuable metal recovery [3]."

Jan 1, 2014

By Emil B. Milosavljevic

Problems associated with distillation and other classical methods for analyzing operationally defined cyanide (CATC, WAD, Total and Free Cyanide) will be discussed. These methods often achieve incomplete, species dependent cyanide recoveries and suffer from serious interferences. Depending on the relative concentrations of interferents and other matrix constituents, underestimation (ultimately Type II errors probability of not detecting a constituent when it is actually present) or overestimation (ultimately Type I errors -probability of deciding a constituent is present when it is actually absent) of the cyanide levels present in a ,given sample may occur, causing in the first case false security and in the second case, excessive cyanide treatment costs. Mahy, if not all, enumerated problems can be solved by using novel flow injection (FI) gas-diffusion amperometric methods. A modification of the recently approved FI ligand exchange (FIILE) method for determination of available cyanide (USEPA Method OIA-'l677) that obviates sulfide interference will be discussed. Eight laboratory round-robin data obtained for the FI UV -digestion (FIIUV) method that determines total cyanide (Proposed Method OIA-1678) will also be presented. In addition, some methods for cyanide speciation will be presented. Finally, research needed for developing reliable methods for determination of operationally defined cyanide in solid samples will be summarized.

Jan 1, 1998

By J. Daniel Bryant

Deformation processing of rapidly solidified powder alloys presents a technical challenge different in several ways from the processing of ingot based alloys. The metastable phases formed during planar flow casting of aluminum alloy 8009 (FVS0812) must be safe-guarded from high temperature excursions during processing to avoid decomposition; this restriction prohibits liquid phase sintering of particles during consolidation. The development of strong particle-particle adhesion, therefore, relies on the imposition of very large strains during forming operations to insure sufficient mechanical meshing of the aluminum particles and break-up of prior particle oxide boundaries. These strains are generally much greater than those required for metallurgical transformations in ingot based alloys. In an attempt to quantify the deformation required to improve interparticle bonding, the finite element method (FEM) was employed. Preliminary results which predict the metal flow and strain distribution in several workpiece configurations are discussed. These predictions are then correlated to measurements made on experimental subscale forgings. Lastly, experimentally measured quantities which reflect the degree of interparticle bondingg are related back to FEM model predictions.

Jan 1, 1992

By George S. Dulikravich

An advanced semi-stochastic algorithm for constrained multi-objective optimization has been adapted and combined with experimental testing and verification to determine optimum concentrations of aJ10ying elements in heat-resistant and corrosion-resistant H-Series austenitic stainless steel alloys. The objective was to simultaneously maximize a number of alloy's mechanical properties. This research will result in a rigorous tool for the design of high-strength H-Series steels and other types of alloys unattainable by any means existing at the present time. Such a material-by-design tool will also be able to reduce or minimize the need for the addition of expensive elements such as Cr, Ni, Co, Nb, Ti, V, etc. and still obtain the optimum properties of an aJ1oy.

Jan 1, 2003

By David A. Neudorf

Known resources of nickel laterites considerably exceed nickel sulfide resources and there is a growing consensus that most new nickel production will be sourced from laterites. The development of nickel laterite projects is very capital intensive due to inherently low grades, inability to concentrate ore prior to processing, complex processing technology and typically large infrastructure requirements. This has resulted in most recently proposed projects being "mega-projects," to achieve economics of scale. However, this may result in unacceptable project risk in many cases. Furthermore, many known laterite resources are not large enough to support a mega-project. This paper describes an alternative model for nickel laterite project development that allows, smaller scale and reduces capital exposure. The requirements of this model in terms of process technology, infrastructure and commercial innovation are described. Keywords: Nickel, Laterite, Project, Economics

Jan 1, 2004

By Michael S. Moats, Scott C. Campin, J. Brent Hiskey

"Electrochemical techniques are a valuable means of analyzing the passivation of commercial copper anodes. Electrochemical impedance spectroscopy (EIS) provides information concerning transport and reaction phenomena occurring at an electrode surface. Commercial. copper anodes of varying compositions have been examined using EIS. Experiments were conducted in a flat cell with an electrolyte of 40 gil Cu2 + and 160 gil H2S04 maintained at 65 DC. Impedance spectra were obtained at the potentials characteristic of the open circuit voltage and passive region for each anode. The spectra of the passivating films exhibited a flattened resistive/capacitive loop at middle to high frequencies and an inductive loop at low frequencies. An equivalent· circuit utilizing an inductor-resistor series in parallel with the double layer capacitance and charge transfer resistance was adequate in modeling the impedance data. The influence of anodes impurities on the components of the equivalent circuit is discussed and correlated with a hi-layer passivation model.IntroductionPassivation of copper anodes during industrial electrorefining has received considerable attention in the past few decades. Great strides have been made in understanding the roles of anode impurities [1-25], electrolysis parameters [20,26], and electrolyte chemistries [20,26]. Even so, passivation still occurs even in the most modem of refineries. The exact cause of passivation is not fully understood. It is known that the anode surface becomes covered by a passivating film. This film has been proposed to be CuS04'&5H20, Cu20, or mixed oxides. The localized concentrations of Ft, Cu+, and Cu2+ ions determines which phase is more favorable. The presence of these ions is controlled by the reaction kinetics and diffusion of species through the slimes layer.Reaction kinetics between Cu, Cu +, and Cu2+ are based on the dissolution mechanism of copper. There exists four different models to describe the dissolution of pure copper. The classical model of Mattsson and Bockris [27] involves two single electron transfers with the cuprous-cupric reaction being the rate detennining step. More recently, Wong, Collier, and MacFarlane [28] used ac impedance to elucidate a more complex mechanism involving the affect of pH and anions. Their findings indicate that the formation of cuprous ions in solution, Cu(I)so~ is favored over Cu(1I) ions adsorbed to the electrode surface in the presence of sulfate and as pH increases from pH 1 to pH 5."

Jan 1, 1997

By M. Omneya El-Hussaini, M. Galal Abdel Wahab, A. Mohamed Mahdy, M. Fathi El Shahat

"Um-Gheig Pb-Zn representative sample was collected from the main adite of Um-Gheig mine along Red Sea coast in Egypt. Its chemical analysis shows that, it contains 16% Zn, 2.3% Pb, 0.1% Cd and 0.1% B as elements of interest. After H2SO4 agitation leaching, the chemical composition of Um- Gheig Pb-Zn deposit ore residue assayed 2.26% Pb, 1.5% Zn, 0.085 % B and 0.01% Cd. This residue was leached with 20% HCl at S/L ratio 1/3 for 2 hours at 80o C. The chloride leach liquor was found to contain 18 g/l Pb, 13 g/l Zn, 0.1 g/l Cd and 0.75 g/l B with the corresponding leaching efficiencies 79%, 86%, 100% and 88% respectively. Lead was precipitated from the chloride leach liquor using concentrated H2SO4 to obtain PbSO4 with precipitation efficiency 96%. While boron was extracted by the selective resin Amberlite IRA743 with loading efficiency of 80%. On the other hand, Zn and Cd were precipitated using Na2S solution with 86.7% and 100% recovery efficiencies respectively.IntroductionLead-zinc ores occur in Egypt in a few localities distributed along the Red Sea coast between El Qusier and Ras Banas.. The reserve of the ore deposits has been estimated by Soviet and German Experts to be about 900,000 Ton, [1]. Onal et al., [2] recovered Pb from Pb–Zn sample containing 10.17 % Pb and 10.98 % Zn from Aladag in Turkey. El-Sherif, [3] used concentrated HCl to leach lead-zinc ore sample of Um-Sammuki area in Egypt. As had been published by Marchioretto et al. [4], the precipitation of heavy metals with lime, sulfide and caustic soda are the most commonly used economical methods for metal removal. Lead was completely removed from the anaerobically digested sludge by precipitation with NaOH and Na2S at waste water treatment plants. Mahdy et al., [5] had successfully extracted boron from the bittern solution of Qaron Lake by ion exchange resin (Amberlite IRA 743). The extraction of boron was mainly depending upon the pH value. They extracted 80% of boron at pH 5.5, while at pH 3.9 about 74% boron was extracted. Kabay et al. [6] used the column-mode to remove 1g/l of boron from geothermal waste water of the Kizildere-Geothermal Power Station by using Diaion CRB 02 Nglucamine- type chelating resins. In this regard, the removal of lead, cadmium and boron allow the residue to be reclassified as non hazardous material."

Jan 1, 2008

By André L. B. Bittencourt

The copper content in the waste slag represents the greatest loss in the process of Caraíba Metais' Smelter. By identifying the variables responsible for copper stabilization in the slag, a minimization on these losses is expected, producing a granulated waste slag with a copper content lower than 0.7%. Statistics resourses such as control charts, Pareto's diagram and correlations curves were applied for the data obtained in the first semester of 1992. The magnetite and the calcium oxide contents in the slag of the Flash Smelter Furnace were most prominent variables. Some operational changes introduced during and after this investigation have shown good results.

Jan 1, 1994

By C. S. Simons

This paper presents a review of the extractive processes used in the production of nickel, with emphasis on developments since the beginning of the Second World War. Attention is given to the factors, many outside the nickel industry itself, which determined the direction of process research and strongly influenced the ultimate commitments to industrialize the resulting developments. An example of such a factor is the sudden surge in demand, far exceeding the then available nickel production capacity, that was caused by the advent of World War II; the result was the first serious consideration ever given to low- grade laterites as a viable source of primary nickel. Other factors discussed include such items as process development in the extraction of other metals - particularly copper; the availability of increasingly sophisticated materials of const- ruction; the advent of the "environmentalist" and related political developments; the massive escalation in the price of energy - particularly oil. The paper concludes with an attempt to forecast the nature of the most effective nickel process of the future, based on extrapolation from the economic and political situation that exists today.

Jan 1, 1988

By R. Tunold, Y. J. Zhang

"The cathodic kinetics of aluminum deposition from aluminum chloridealkali chloride melts was studied by use of electro-cnemical transient techniques at 700 °C. Aluminum deposited as an insoluble product on a glassy carbon electrode and as a partly soluble product on a tungsten electrode. The deposition was found to be a simple diffusion controlled process involving the exchange of three electrons. The diffusion coefficient of aluminum chloride was calculated - 4.sx10-s cm2 ·S-I in AlCl3 -NaCl-LiCl melts and 2.6x10-s cm2 ·S-' in AlCl3 -NaCl-KCl melts. For AlCl3 -NaCl-CsCl system the diffusion coefficient exhibited some uncertainty due to nucleation. The determined rate constant of aluminum deposition reaction was on the order of 10-' -10-2 cm'S:' Constant potential electrolysis was carried out. TiB2 was well wetted by aluminum. The species of melts penetrated into graphite and glassy carbon but not into tungsten. The diffusion coefficient of species in glassy carbon was evaluated.IntroductionAluminum chloride electrolysis is attractive for its power saving of 30%. Different process to circumvent the conventional chlorization to obtain aluminum chloride economically, such as directly chlorizating mixture of Al~03 and C in a cell with A-shaped laminated bipolar electrodes by rising chlorine (1), or by use of a composite anode (2), will promote the electrolysis technology to be realized industrially. With the appearance of the Alcoa process periodically there are studies on the kinetics of aluminum deposition. Some discrepancies seem to exist on the mechanism of aluminum deposition. Borne studies (3,4,5) showed that the deposition of aluminum was hindered by diffusion process in the melts. M.Gabco et a1. (6) claimed a preceding dissociation of a complex being the rate controlled step. This paper presents our results on the mechanism of aluminum deposition from the study by use of transient techniques and some results from constant potential electrolysis."

Jan 1, 1988

By Rainer Schmid-Fetzer

"Isothermal solidification can be used to form strong bonds at low temperature which remain solid at much higher temperatures. The exploitation of this principally known technique for new high temperature processing steps and applications in electronic assemblies is the aim of this study. Three basically different variants of this bonding process are given. A comprehensive metallurgical screening is performed and the feasibility of binary material systems is given on a quantitative scale. Very attractive systems are spotted that have never been studied before. Detailed examples for the realization of bonding with complex ternary and multilayer systems are given. A highly innovative example is the chip stack or wafer to wafer bonding of unmetallized Si or SiC at 250°C. The proposed bond remains stable above the melting point of Si and enables entirely new semiconductor manufacturing steps. An improved die bonding process was proposed and verified experimentally.1. IntroductionIsothermal solidification can be applied to form strong bonds at relatively low temperature which remain solid at higher temperatures. The general principle of this type of joining processes is illustrated in Fig. 1. An interlayer of a low melting component, Lo, is provided as a foil or a thin film coating between the high melting joint components, Hi. The assembly is heated under moderate pressure to the bonding temperature, T 8 , and a liquid filler forms, either because the melting point of Lo is exceeded or due to a eutectic reaction between Lo and Hi. This molten filler initiates a rapid interdiffusion or reaction diffusion between Lo and Hi and the subsequent approach to an equilibrium state results in isothermal solidification. The solid phases formed at T 8 in the joint region exhibit a remelt temperature above T8 •"

Jan 1, 1996

By I. Gaballah

Jarosite contains up to 15 % of heavy metal compounds 'HMC'. The current waste disposal methods will not be allowed in the near future due to new environmental regulations and pollution risks. For these reasons, thermal treatments of raw or decomposed jarosite, in controlled atmospheres, were investigated. The aim of these treatments is to decontaminate the jarosite and/ or to recover the HMC for recycling. According to physico-chemical characteristics of the samples, the thermal treatments in controlled atmospheres N2, CO+N2 and C12+air lead to the extraction rate that vary from 93 to 98 %. Heavy metal compounds were separated by cooling the gaseous phase. The treatments' residue was almost free from HMC. Between 700 "C and 800 "C, the chlorinating treatment was successful of eliminating more than 97 % of HMC contained in four different samples.

Jan 1, 1999

By P. Halsall

Smelters of medium or low grade tin concentrates must recover a high proportion of tin from iron-bearing slags or concentrates; the volatility of tin sulphide makes possible the production of iron-free tin fume. Laboratory work defined conditions which would promote the sulphidisation of tin slags and concentrates melted with them, to result in tin recovery as fume, and a residue of less than 0.5% Sn content, which could be controlled to vary with the value of tin. Subsequently pilot-plant work on 6-tonne and 15-tonne scale led to a commercial plant of 45 tonne. capacity (1962), for melting and fuming primary and secondary low-grade tin materials by submerged combustion. Some factors contributing to the rate of Working expressed in terms of the 'half-life and the amount of work done, the 'half-life-tonne' are studied, leading to the design and operation (1972) of the 100-tonne water-jacketed unit, presently in use, treating a wide range of slags and low tin-content ores and residues.

Jan 1, 1983

By Mototsugu Matsuno

A new process has been developed to treat fly ash generated from municipal incinerators, which contains not only toxic metals such as lead and cadmium, but also dioxins. The process includes the following steps; fly ash is formed into green pellets with some additives and the pellets are then roasted to eliminate or stabilize the toxic metals and to decompose dioxins. A pilot plant with a capacity of approximately 100 kg/hr was used to test the process. The tests verified that heavy metals were either volatilized or stabilized and dioxins were decomposed by high-temperature roasting. The pelletized ash was found to be non-toxic, so that it can be recycled as artificial lightweight aggregate. It was also found that volatilized metals collected as secondary ash can be recycled as smelting resources.

Jan 1, 2003

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 S. Seetharaman

In the processing of molten metals, it is extremely important to monitor continuously the concentration levels of various minor elements, In the production of common metals like copper, iron and aluminium electrochemical sensors involving solid, as well as liquid electrolytes are being increasingly used to measure the concentrations of minor elements The present paper deals with the electrochemical principles underlying these measurements and the possible errors involved. One of the major difficulties in the case of the solid electrolytes is to correct for the consequences oldie electronic contribution to the conduction of the electrolyte. The application of the electrochemical sensors for molten metals processing involves designing of these probes to withstand the industrial operating conditions. In this respect, significant achievements have been made with respect to the design of oxygen probes for liquid metals in general and liquid copper in particular. Some of the salient design features are discussed in the paper, The application of auxiliary electrodes for impurities in molten metals like phosphorus in copper and silicon in iron are taken up. The development of oxygen sensors for slags is given special attention. Recent developments' in the field of sensor technology, as applied to metals processing are highlighted.

Jan 1, 1996