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By L. E. Murr

Preliminary studies of bacterial attachment to MoSp (molybdenite) have indicated a low correlation between dislocation density in the (0001) basal plane and the density of attached microbes. In the present investigation, poly- crystalline thin sections of CuFeSp (chalcopyrite) have been ion-etched or carefully comminuted to electron transparency and observed in the transmission electron microscope. The thinned test sections were then immersed in a culture solution in which bacterial attachment occurred. The attached bacteria were biologically stained in a uranyl acetate solution and the entire thin CuFeSp sections or tiny particles containing thin, electron transparent edges with bacteria attached were observed in the transmission electron microscope, allowing the coincidence of bacteria and their density to be directly observed in relation to lattice dislocations and crystallographic orientations of the exposed surfaces. This technique has the advantage of exposing crystallographic orientations where dislocation lines intersect the free mineral surface, and the emergence sites of dislocations could in principle be directly investigated as a possible preferential attachment site for bacteria. Bacteria morphologies were also extensively observed in the scanning electron microscope. The implications of the results are that although a strong correlation between dislocation density and distribution and bacterial attachment, density, and distribution has not been established, systematic multiplication of dislocation densities in crystalline mineral particles to be leached could enhance leaching rates by increasing the reaction rates as well as the density of attached bacteria at crystalline, metal-rich phases. Techniques for dislocation production in mineral and ore bodies and the particular implications in chalcopyrite leaching are discussed in relation to in-situ leaching where comminution is attained by explosives and the generation of strong shock waves in an ore body. The present study demonstrates the use of microanalytical and microscopic techniques in the investigation of fundamental microstructural phenomena in hydrometallurgical processes.

Jan 1, 1976

By H. K. Lin

Thermodynamics of Cu-C1-H2O system and the kinetics of copper dissolution in cupric chloride solution were studied with emphasis on possible difficulties which may occur during copper electrowinning. E,-pC1 diagram of this system wasestablished. Equilibriumdistributionof various copper chloride complexes of different valent states at the presence of metallic copper was computed through the relations of the simultaneous equilibria. The mechanism-of copper dissolution in the cupric chloride solutions was proposed and the mechanism of copper electroposition was discussed. The researched results were used for guiding the investigation of copper electrowinning from cupric chloride solution.

Jan 1, 1991

By J. Dille

Metallic cobalt exist in two allotropic forms : the hexagonal compact a which is stable at low temperature ( ( 420') and the cubic form 0 stable at higher temperature. This latest form is the only one which is ductile. During the electrode position of Co, in moderate acidic conditions, we noticed a code position of both a and B forms. The influence of several parameters on the B/a ratio in the deposit was investigated. High acidity and the presence of Fe increased its ratio; on the opposite, high temperature promote the a phase. No significant influence on the material were noticed. The differentiation of a and B forms of Co is rather difficult and the method of J. Scoyer was improved quite successfully.

Jan 1, 1988

By John Nauman

Liquid ferrous silicates that are related to cop- per slags have been studied as media for the transfer of heat in pyrometallurgical processes. The effective thermal diffusivities have been measured from 1025Oto 1400°C, and values in the range of 0.004 to 0.007 cm2/ sec have been obtained. The heat-transfer characteristics of these slags have been determined by measuring the rise of temperature of a cold nickel sphere immersed in the liquid slag. The sphere is spun about its vertical axis to obtain a well characterized flow of liquid about the sphere. The principal barrier to the transfer of heat from the bulk slag to the metal sphere is a solid shell of slag that forms around the sphere and subsequently melts. It appears that the detailed nature of this shell is important to theheat- transfer process. A mathematical model is used to predict the rate of heating of the sphere, and to evaluate various aspects of the system that can influence the transfer of heat.

Jan 1, 1976

By John C. Taylor

With growing emphasis on energy conservation and increased concern over the presence of heavy metals in the environment, it is fortunate that most metals are readily recycled. In this respect, metals have a significant advantage over plastics and similar materials used as metal substitutes. For many years a secondary industry has processed scrap copper, nickel, lead and zinc to produce refined metal which has, to varying degrees, influenced the price and displaced the production of primary metal. This paper reviews some of the challenges the industry will face and the changes in process technology which will be required as pressure mounts to increase the amount of metal recycled. In the case of most base metals, this will have an impact on primary metal production; as the tonnage of metal recycled increases, the requirement for primary production, or new metal, will depend more and more on the growth in consumption.

Jan 1, 1993

By L. W. Beckstead

The use of acid ferric sulfate solution as a lixiviant for chalcopyrite concentrates has been of little interest from a practical standpoint due to the formation of a tenacious layer of elemental sulfur which severely impedes the reaction progress. CuFeS2 + 4Fe+3 ?Cu+2 + 5Fe+2 +2s° For example, an acid ferric sulfate leach of chalcopyrite concentrate results in only 12% copper extraction in a three hour leach at 93°C. Experimental results suggest that particle size is the only controllable variable which has a significant effect on the rate of acid ferric sulfate leaching at ambient pressure. Size reduction of the concentrate prior to leaching was exam¬ined using various methods of grinding. Of the grinding methods considered, attrition grinding was found to be the most effective. Leaching of an attritor-ground product (median particle size 0.5 microns) resulted in approximately 90% copper extraction in a three hour leach at 93°C. Energy measurements suggest that the costs associated with attrition mill¬ing are not unreasonable. Evidence indicates that "activation" or stored strain energy is not responsibile for the enhanced reaction kinetics of the finely ground concentrate, but rather the experimental results can be explained simply in terms of the increased surface area due to size reduction. Leaching reaction mech¬anisms operative in the acid ferric sulfate system are discussed and the application of ultra-fine grinding technology to other systems is considered.

Jan 1, 1976

By Peter Brown

The present work involves the study of Chemical Vapor Deposition (CVD) of silicon carbide from the methyltrichlorosilane (MTS) - hydrogen system. A computer program, SOLGASMIX has been employed to calculate the equilibrium compositions of the gaseous and condensed phases in the MTS - H2 system. The results indicate the range of parameters such as temperature, pressure and species concentrations, required to deposit the single phase Sic under thermodynamic equilibrium conditions. A mathematical model for describing the transport phenomena and the rate of deposition of Sic onto a thin rod in a vertically-oriented hot-walled CVD reactor has been developed. Exper iments were conducted using the same operating conditions as those used in the model in order to validate the mathematical predictions. The predicted rates of deposition were found to be in good agreement with those obtained experimentally. The model can be used to study the effects of various operating parameters on the rate of Sic deposition on a fiber.

Jan 1, 1992

By Hang Goo Kim

A mathematical analysis based on equilibrium modeling has been developed to describe the distribution behavior of minor elements such as Pb, Zn, Bi, Sb, and As among gas, slag and recovered copper phases during the reduction of copper oxide in slag cleaning with CO gas. The results show that large fractions of the impurities transferred to slag during smelting or converting are recycled to the recovered copper metal. It is also shown that there is a limit to the recovery of copper from slag because iron oxides are also reduced to form a copper-iron alloy at low oxygen potentials. The effects of various operating parameters such as temperature, the activity of FeO, the initial amounts of the elements in the slag and CO content in process gas, on the behavior of these minor elements are discussed. The predicted results were compared with the results of a pilot plant operation in which pulverized coal was used as a reductant. Consistent trends between the two cases were obtained.

Jan 1, 1992

By E. O. Stensholt

The Hybinette electrorefining process for production of cathode nickel was in use at Falconbridge Nikkelverk A/S, Norway, until 1975 when conversion to the new chlorine leach process was started. In 1978 the conversion to electrowinning had been completed, but further major improvements to the process have been made up to 1987. After a major expansion program in 1985 - 87 the refinery has a nickel capacity of 54 000 mt Ni/year. The main feed materials to the process are converter matte from the Falconbridge smelter in Sudbury, Ontario, Canada, and from the BCL smelter in Selebi-Phikwe, Botswana. A typical composition of the mixed feed to the refinery is: 40 - 45% Ni, 25 - 30% Cu, 20 - 22% S, 2 - 3% Fe and 1.0 - 1.5% Co. The matte is chlorine-leached in the first process step, nickel being dissolved selectively in a train of leach-cementation tanks. Essentially all copper and sulphur that was present in matte appears in the leach residue as CuS. In 1986 an autoclave treatment stage was added to the process to improve nickel extraction from the leach residue. The resulting strong nickel chloride solution is purified by the process steps (1) precipitation of iron and arsenic, (2) solvent extraction of cobalt and other minor elements and (3) precipitation of lead and the remaining impurities. The nickel solution is then fed to the tankhouse, where various nickel products are produced by electrowinning. The chlorine gas that is produced during the electrolysis is returned directly to the chlorine leaching tanks to dissolve more matte. After stripping from the loaded organic phase and solution purification cobalt is also produced by electrowinning. The copper sulphide leach residue, which contains some nickel, is dead- roasted in fluidized-bed roasters. The sulphur is recovered and sold as sulphuric acid. The calcine is leached in spent copper electrolyte, from which cathode copper is produced by electrowinning. Precious metals and the remaining base metals are recovered from the copper leach residue. The Falconbridge chlorine process is very versatile. It can accept a wide range of impurities in the feed and still produce metals of exceptional purity.

Jan 1, 1988

By R. G. Robins

Metal separations based on the selective precipitation of phosphates have a potential application in many hydrometallurgical processes. This paper reviews the literature on the solubility of a number of both divalent and trivalent metal phosphates and presents the result of some additional experimental measurements. The systems examined have been modelled to obtain free energy of formation data for the various species. Computer generated solubility diagrams which are described can be useful in predicting a variety of metal separations.

Jan 1, 1991

By F. Sekula

Tetrahedrite and siderite are two main valuable minerals present in the silver Mária Bana deposit. The tetrahedrite concentrate prepared from it by flotation has certain specific properties from the metallurgical point of view. Siderite is concentrated in the flotation tailings. The paper presents results of the laboratory and pilot-plant testing of the combined hydrometallurgical and pyrometallurgical methods proposed for treatment of the tetrahedrite concentrate and siderite waste. The testing conditions were based on thermodynamic analysis of the reactions that proceed in the process. The proposed technology makes it possible to separate copper from sulphur, mercury and iron in a straightforward way. Copper, after its refining, can be subsequently treated in the finishing operations. At the same time it is a valuable source of precious and noble metals. The siderite-containing flotation tailings can be converted to iron of the technical purity and slag. The proposed method is a good starting point for the development of the closed-cycle technology.

Jan 1, 2006

By B. Yawney

A copper-nickel sulfide concentrate was leached in water at about 2000C under oxygen pressures of about 0.35 MPa. Oxidation of sulfide to sulfate was virtually complete in about 30 minutes, resulting in greater than 95% copper and 98% nickel extractions. Leaching temperature was shown to be the most important factor affecting metal extractions. Measured rates of oxygen consumption were used to develop batch kinetic data. Mini-plant continuous pressure leaching tests agreed with batch leach results. A proposed overall flowsheet is briefly examined.

Jan 1, 1976

By X. J. Wu

Effects of various factors such as diaphragm materials, composition of electrolytes and current density on copper electrowinning from cupric chloride solutions was investigated. It is found that the crux of this process is to prevent the dissolution of copper by cupric ion and the formation of suspended CuCl precipitate. A process with high difference of copper concentrations between the feed solution and the spent electrolyte was selected. With this process, in which the feed solution contains 90 g/dm3 [Cu"], 3M NaC1, and 10mg/dm3 bone glue, and the spent electrolytes contains 10 g/dm3 [Cul, a very smooth and dense copper cathode can be produced with current efficiency above 93% and energy requirement less than 1.7 kwh/kg Cu at 25°C with N2 sparging. If a slightly higher energy requirement is permitted, smooth and dense copper cathodes can be produced at the current density up to 800 A/m2 with the identical solutions.

Jan 1, 1991

By Douglas J. Harvey, Chi-Mou Ni

"This paper presents an analysis technique for the solidification of metal castings. This method, based on a modified finite difference scheme with an irregular mesh, is capable of dealing with the complex geometries of castings. The nonlinearities in material properties of specific heat and thermal conductivity, arising from the phase change during solidification, are accounted for in the step-by-step calculations. Two solidification problems are solved with this analysis technique and the calculated results compare satisfactorily with experimental data. IntroductionCasting process design engineers are often faced with the difficult problem of designing castings to be produced porosity-free. Since the solidification of metal is affected by many interacting variables such as the thermal conductivity, density, and specific heat of both the molten metal and the mold, it is easily seen why this is a difficult task.Typically, casting tooling design is an intuitive process which builds on past successful methods. After processing equipment is constructed, trial castings are made and examined for dimensions and integrity. Changes in the tooling are generally required to improve casting soundness or to reduce cycle time. In the permanent mold process, tooling is complex and difficult to alter after initial construction. The water-cooled steel molds are part of the complete automated system. Associated holding furnaces, pouring ladles, casting conveyers, and utility connections all make other than minor adjustments a costly and time consuming task. An analytical method for using the principles of heat transfer for predicting solidification patterns would be of great value in the permanent mold process by minimizing costly changes."

Jan 1, 1986

By R. W. Lawrence

A method by which it is possible at an oxidation potential below 680 mV SHE to achieve quantitative conversion of sulphide sulphur to elemental sulphur instead of sulphate in a biological leach of chalcopyrite and bornite has been investigated. The process chemistry, biological phenomena and process flowsheet options are discussed. Several copper concentrates have been evaluated and have been found to be amenable to th process. Results to study the progression of chalcopyrite decomposition during the leach are presented and mineralogical factors affecting the requirement for silver addition are discussed. A chloride addition method for improving silver recovery is described. The results of a small scale continuous leach test have demonstrated that continuous operation can be carried out with high copper extraction and stoichiometric conversion of sulphide sulphur to elemental sulphur.

Jan 1, 1985

By U. M. Mutnti

In order to meet the stringent market requirements for high purity cobalt, ZCCM commissioned the VIR plant in December 1982. The plant comprises a 4.1 tonne/heat vacuum induction furnace with a rated annual capacity of 2,500 MT of barstock. In the VIR furnace, molten cobalt is held under vacuum at 1600°C resulting in the removal of more volatile impurity elements by distillation. Operations todate have demonstrated that Pb, Zn and Cd have good distillation rates in excess of 95%, leading to cobalt containing 1 ppm or less of the above elements. Removal of other impurities such as Se, Bi is about 65% with the finished product still assaying around 1 ppm of each of these elements. Vacuum refining of cobalt offers an economic route for producing higher grades of cobalt from the type of concentrates and treatment processes available within ZCCM. The consistency of VIR cobalt quality has been confirmed by ZCCM and some of its alloy customers.

Jan 1, 1988

By A. P. Paiva

Although the advantages of Solvent Extraction for separation/purification of relatively concentrated solutions are well known in Extractive Metallurgy, its use for the recovery of elements present in low levels only recently has been discussed, with particular attention devoted to precious metals. In this work, the extraction behaviour of Cyanex 471X towards silver, from an acidic chloride medium is reported, the extraction and stripping isotherms and related kinetic features analysed. Results on the selectivity of silver extraction against high contents of iron, copper and lead are discussed. Phosphine sulphide extractants are generally associated with solvation mechanisms: analysis of the extraction pathways along with the possibility of reaching a suitable loading in the organic phase are also presented.

Jan 1, 1993

By Uday B. Pal

In the electrochemical vapor deposition (EVD) process, gaseous cation precursors are passed over one side of a porous substrate, and oxygen is passed on the other side of the substrate. The gases diffuse and react within the porous substrate, and the pores get filled with the desired solid oxide. Subsequent solid state electrochemical transport through the solid oxide in the pores continues the reaction, and the film grows over the porous substrate. The EVD process has been used to deposit lanthanum chromite interconnection films and yttria stabilized zirconia electrolyte films over porous air electrodes. The EVD growth of these solid oxide films is found to be parabolic in nature, which indicates that the solid state transport (diffusion) of ions through the film controls the growth. This solid state transport can be analyzed using Wagner's treatment of the electrochemical transport. Conductivity measurements and the information on the defect structure of the oxide can be combined with the EVD growth rate measurements to calculate the solid state transport properties (transport numbers and partial conductivities) of the rate-controlling minority species in the oxide. Using this approach, the EVD growth of other electronic, mixed conducting and ionic solid oxide films can also be analyzed.

Jan 1, 1992

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

The merging of flash smelting with spray converting in one single furnace is proposed as a continuous copper making process. The proposed process is expected to produce blister copper, clean slag and gas with high sulfur dioxide concentration. Some high grade matte is an intermediate product recycled within the proposed furnace, spray-atomized and converted. The thermodynamic equilibria of the simultaneous oxidations which take place during copper smelting and converting are discussed in order to establish the gradient of oxygen potential along the furnace required for smooth operation. The proposed process is a dynamic system designed to reach equilibrium only close to the slag skimming end of the furnace. The process feasibility is based on the predesigned significant difference between the rates of converting reactions in a finely dispersed system and the rates of deconverting reactions between immiscible liquid phases of restricted interface area. The converting of small stationary droplets of matte, in a silica saturated system, was studied in the laboratory for extremely short oxidation times (10 to 120 seconds). These experiments led to some interesting observations on reaction mechanisms and kinetic trends. The droplet size and the matte grade affected very strongly the oxidation rate and the proportion of the different products obtained.

Jan 1, 1976