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By Y. K. Rao

In the carbonyl process for the refining of crude nickel CO(g) reacts with nickel in the 310-370K range producing nickel tetracarbonyl, Ni(C0)4(g). Iron and cobalt impurities also form gaseous carbonyls but their partial pressures are low. The carbonyl is led to a decomposer plant wherein the gas disproportionates in the 500-600K range depositing pure metal on nickel pellets that move countercurrent to the gas-flow. This system serves to illustrate the fundamental principles involved in the vapor phase mass transport of elements, against temperature-gradient, under the influence of chemical potential gradient. Unlike in the crystal growth, the source is at a lower temperature (say 350K) whereas the seed is in the hot-zone (say 550K) of the closed ampoule-type reactor. By assuming virtual gas-solid equilibria in the end zones, with diffusion of gaseous species between them acting as a slight perturbation, the quasi-steady- state mass-transport rates are computed for a range of CO-pressures and temperatures.

Jan 1, 1993

By P. M. Prasad

The last two decades have witnessed the emergence of numerous hydrometallurgical and direct processing techniques for the extraction of some metals from pocketed/lean/complex sulfide ore deposits. A new approach with some inherent technological merits, investigated in recent years, is the lime-enhanced reduction of metal sulfides. Thermodynamic aspects relevant to the lime-enhanced reduction of metal sulfides by H2,C0 and C are discussed. A survey of the researches on the basic features of and factors influencing the lime-scavenged reduction of selected sulfides and sulfide concentrates reveals that lime tremendously enhances the sulfide reduction rates (up to 100 times) and drastically reduces the sulfur emission into off-gas to negligible levels. Further successful practice of lime-enhanced reduction requires only a moderate temperature of reduction (characteristic of each sul¬fide) and, in the case of gaseous reduction, relatively low gas flow rates. Relevant kinetic aspects of the concerned reactions that have a bearing on process development and its understanding are also briefly discussed. A conceptual scheme of general applicability for the processing of sulfide concentrates by the lime-enhanced reduction technique consists of three main steps: (0 lime-enhanced reduction by a suitable reagent (e,g., H,2, CO, gasified coal, water gas), (ii) separation of the product metal from the dry slag (CaS + unused CO) by mechanical separation, magnetic/gravity concentration or flotation and (iii) melting and refining by standard procedures. This novel approach, which is patently less complex, is expected to employ basically simpler flow sheets at comparatively lower operational temperatures and aid in pollution abatement. Potential for developing such a route for the small scale extraction of metals like copper, molybdenum and antimony is indicated. Possibility of utilizing this technique for the production of fibers/ filaments of some metals is also outlined.

Jan 1, 1983

By Florian Kongoli

Non-ferrous smelting slags .can contain magnesia, which substantially increases the liquidus temperature. One option to counter this increase is to flux with calcia. In this work, experimental liquidus measurements including new measurements on industrial slags have been compared with a FACT-based thermodynamic model, which predicts the liquidus surface of multi-component iron silicate smelting slags containing both magnesia and calcia. The predictions, which agree well with experimental results, are summarized in both isothermal and non-isothermal diagrams to give a quantitative description of the liquidus surface.

Jan 1, 1998

By A. Dutta, B. Devulapalli, A. Mukhopadhyay, E. W. Grald

"Computational Fluid Dynamics (CFO) has matured over the past two decades as an analysis tool for conducting virtual experiments with significant time and cost savings. It complements and reduces physical testing. CFO has penetrated the diverse materials industry in much the same way as Computer Aided Design (CAD) did more than a decade ago. As the basic numerical algorithms used in CFO have steadily improved, so have the reliability, consistency and user-friendliness improved significantly, too. Other recent trends have also contributed to the rapid growth and widespread adoption of CFO. In this presentation, CFO applications from several materials processing industries will be presented using case studies. Emphasis will be on metals, glass and semiconductor applications.IntroductionThe term materials processing covers a diverse array of industrial applications and products today. From the continuous casting of steel, to the deposition of semiconductor materials atom by atom, to the extrusion of molten polymers, materials processing applications span an incredible range of length scale, process times, pressures, temperatures and velocities. The properties of the materials themselves, in terms of density, viscosity, thermal conductivity, etc., can be complex functions of temperature, shear rate, chemical composition and time. And the processing equipment may be very complicated in geometric shape.Computational fluid dynamics (CFD), the technique of solving the governing equations of fluid motion and other related phenomena using a computer, has enjoyed widespread and rapid growth, which started in the aerospace and automotive industries. More recently, CFD has also been successfully applied to a great many materials processing problems, in spite of the challenges described in the previous paragraph. The reasons for the growing usage of CFD in materials processing are many. Using CFD to test design options and reduce the number of physical prototypes can decrease the time and cost associated with new product and process development. CFD gives insight and provides detailed predictions of operating conditions in lieu of difficult, intrusive and often expensive experimental methods. CFD can be used as an aid to scale-up processes from lab or pilot scale to full production. Troubleshooting the performance of existing equipment is often carried out with the help of CFD. Determining how an existing piece of process equipment will operate under new conditions, or with new input ,materials, is also a common task for CFD."

Jan 1, 2004

By Neng-Wen Yu, Shau-Jun Zhu, Ji-He Wei

The desulfurization process by powder injection and blowing in the RH refining of molten steel and its mechanism have been considered and analyzed. Based on the two-resistance mass transfer theory and the mass balance of sulfur in the system, a kinetic model for the process has been developed. The related parameters of the model, including the mass transfer coefficients and the effective amount of powder in the molten steel being treated for desulfurization, have been more reasonably determined. Modeling and predictions of the process of injecting and blowing the lime-based powder flux under assumed operating modes with the different initial contents of sulfur and amounts of powder injected and blown in a RH degasser of 300 t capacity have been carried out using the model. The relevant circulation rate of the liquid steel and the powder injection and blowing rate were taken to be 100 t/min and 150 kg/min, respectively. The initial contents of sulfur in the liquid steel to be treated and the amounts of powder injection and blowing were respectively assumed to be 0.007, 0.006, 0.005, 0.004, 0.003, 0.002 mass-% and 10, 8, 6, 5, 4, 3 kg/t-steel. The total treatment time for desulfurization under each mode was set up at 24 min, equivalent to eight circulation cycles of the liquid steel to be treated. The results indicated that the predictions made with this model are in good agreement with some data of the industrial experiments and practice. Injecting and blowing the lime-based powder flux with the composition of 85 mass-% lime (CaO) + 15 mass-% fluorspar (CaF2) of 3-5 kg/t-steel, it is possible to decrease the sulfur content in the molten steel to ultralow level below (5-10)x10·4 mass-% from (60-80)x 10·4 mass-%. The total treatment time needed will appropriately be 12-20 min. Intensifying the powder injection and blowing operation and increasing the circulation rate of the liquid steel may effectively' raise the rate of the process in RH refining. The model may be expected to offer some useful information and a reliable basis for determining the reasonable process parameters and help in optimizing the technology of desulfurization by powder injection and blowing in the RH refining of molten steel.

Jan 1, 2000

By Kuniaki Murase

Cadmium telluride (CdTe) semiconductor has been well investigated as a CdS/CdTe heterojunction solar cell material since its band gap is suitable for energy conversion from sunlight into electricity. In this paper a new electrochemical processing of thin-layered CdTe using basic aqueous electrolytes is reviewed from the standpoint of thermodynamics using a potential-pH diagram. The cathodic electrodeposition of the stoichiometric CdTe with a flat surface morphology took place at more positive potentials than that of the Nernst potential for the bulk-Cd deposition and at more negative potentials than that for the hulk-To. In this potential region deviation from the stoichiometric composition of eleetrodeposited CdTe was controllable by the Cd(II)/Te(IV) concentration ratio, pH, or concentration of complexing agent for Cd2+ ions of the electrolytes, The deposition behaviors for ammoniacal media were well accounted for by the potential-pH diagram of the Cd-Te-NH3-H2O system devised by a combination of those of the Cd-NH3-H20 and the Te-H2O systems, Diagrams for other complexing agents, ethylenediamine and diethylenetriamine, were also constructed to investigate and discuss the electrodeposition conditions regarding the corresponding media.

Jan 1, 2003

By F. H. (Sam) Froes, C. Suryanarayana, K. C. Russell, C. M. Ward-Close

"Far from equilibrium synthesis allows development of novel crystal structures and microstructures, leading to achievement of enhanced physical and mechanical properties. A number of ""far from equilibrium"" techniques are reviewed with emphasis on the amount of departure from equilibrium. The ability of two such techniques, mechanical alloying (MAl, and physical vapor deposition (PVD) to develop novel structures are discussed in detail. For the MA process emphasis is placed on intermetallic compound compositions. Solubility extension, beyond rapid solidification (RS) levels, is found in terminal compositions but not for the intermetallics. Nanostructure-sized grains (< 100nm) form which can be retained after ""low temperature"" compaction. On continued milling in many cases the nanometer-sized grains transform to an amorphous structure. Ordering is destroyed by MA, except in those intermetallics with large negative enthalpies of formation. For the PVD process, a review of application to terminal light alloy compositions is presented. This includes a new high-temperature aluminum alloy, layered materials with nanometer spacing, corrosion-resistant magnesium alloys and low-density titanium compositions. IntroductionTo enhance the mechanical property combinations of advanced structural materials innovations in process/synthesis are required [1-6]. In this paper the capability of various ""far from equilibrium"" synthesis techniques [7,8] to produce novel constitutional and microstructural effects, and hence potentially enhanced physical and mechanical properties, in advanced materials is presented. The application of two such methods, mechanical alloying (MA) and physical vapor deposition (PVD) is discussed in detail. For the MA process emphasis is on intermetallic compositions with consideration given to solid solubility extension, microstructural refinement, amorphization, and formation of intermetallic compounds. For the PVD process application to terminal light alloy compositions is discussed."

Jan 1, 1994

By Forsén. O.

In this ?paper practical solidification of anodes containing nickel, arsenic, antimony and bismuth is compared with the equilibrium? diagrams and kinetic ?factors. In order to clarify the distribution of the impurity elements in the anode the structures were studied after the solidification and also after the electrolysis of anodes. This examination was carried out with optical microscope, scanning electron microscope and electrochemical measurements. All the nickel is remaining metallic in the copper matrix during the solidification and therefore nickel is dissolved in the electrolysis at all oxygen contents, when the nickel content is 0.25 wt-% or less in the anode. The practical .solidification mechanism of the anodes, when the nickel content exceeds 0.25 wt-%, proceeds by the crystallization of nickel oxides. In oxygen containing copper anodes nickel oxide is verified to crystallize together with antimony in certain conditions and to form a micaceous compound (3Cu2O?4NiO?Sb2O5), which may build up a very harmful floating slime in the electrolyte. Arsenic is strongly enriched along the phase boundaries in oxygen free copper anodes. An intermetallic compound Cu3As is formed when the amount of arsenic in the anode. exceeds 0.7 wt-%. This compound is more noble than the copper matrix. This means &apos;that a selective dissolution of copper-arsenic compounds takes place. The copper matrix dissolves more strongly than the grain boundaries. The solidification structures of oxygen free bismuth containing copper anodes show clearly the influence of bismuth. Thin bismuth films which are less .noble than the metallic copper matrix, are formed during the solid1ficatton process. As a result of this the?grain boundaries are dissolved faster than the copper matrix.

Jan 1, 1987

By G. Haesebroek

In L969 Metallurgie Hoboken-Overpelt started an industrial plant for the separation of iron and zinc from a concentrated CoCL2 solution. Iron and zinc are extracted in column contactors by a solvent containing 12 vol % of tertiary amines in xylene. The extracted metals are stripped from the pregnant organic phase by precipitation with a NaOH solution at pH LL. In this paper an overview is given of the industrial process. In order to overcome some drawbacks of this process (low flash point of the diluent, reagent consumption, batchwise stripping) an alternative solvent extraction process has been examined. In this alternative process, iron and zinc are extracted with an or¬ganic phase containing 50 vol % of TBP in Escaid 110. The pregnant solvent is stripped with water in conventional mixer settlers. Despite the ability of this process to overcome most of the inconveniences due to the use of tertiary amines, it suffers from the poor stability of TBP in concentrated chloride solutions, resulting in unavoidable and inacceptable precipitation phenomena in the stripping section.

Jan 1, 1988

By Batric Pesic

Calcium silicate slag (Di-Cal) and magnesium oxide condensate (MgO) are the by-products of magnesium smelting operations, As these oxides have acid neutralizing and metal precipitating properties, it was decided to examine their reactions with (a) individual heavy metals and (b) with a mixture of metals in solution, The resulting solid reaction products were further tested with respect to the stability of the contained metals, The stability of the solid precipitates were examined as a function of the method of precipitation and as function of the solution pH With respect to the method of precipitation, the performance of Di-Cal and MgO was compared to the performance of lime, an industry standard for heavy metal precipitation, Four different pH solutions (4,0, 5,0, 7,0 and 1 LO) were used to study the effect of pH on the stability of the precipitates. It was found that Di-Cal, in most cases, produced the most stable precipitates and thus, outperformed lime, Metal precipitates prepared by the addition of MgO were the most soluble for each metal studied, except for Se,

Jan 1, 2001

By R. S. Celmer

The distributions of cobalt, molybdenum, copper, and selenium between nickel matte and silica-saturated iron silicate slag have been determined in the region of the metallic saturation boundary, at 1523 K. Results are given as a function of the composition of the coexisting Fe-Ni alloy and the activity of iron in the system. Under strongly reducing conditions, these minor elements display a marked preferential accumulation in the sulphide phase. It is shown that the dissolution of cobalt and molybdenum in slag follows an oxidative mechanism, and distribution equilibria are correlated with the oxygen potential. From these data, the thermodynamic properties of cobalt in nickel matte are computed. Further, comparisons of minor element partitions are made between the nickel and copper matte smelting cases under metal saturation conditions.

Jan 1, 1988

By L. J. Lutz

The U.S. Bureau of Mines has developed an electrorefining process to recover Ni, Co, Cr, and other metals from mixed and contaminated superalloy scrap. The superalloy scrap is cleaned then directly electrodeposited as a Ni -Co deposit. The process recovers approximately 90 pct of the Ni-Co available from the scrap as a 99t pct pure Ni-Co alloy. During electrorefining the electrolyte undergoes a purification process which results in Cr and other refractory metals reporting to the purification residue. Operating data is given for a 3-L compartmented electrolytic cell. Techniques for the removal of Fe, Cr, and trace impurities from the recycled electrolyte are outlined. The economics of a facility producing 15 mt/d of a Ni-Co alloy are also discussed.

Jan 1, 1993

By Richard D. Hagni

Microscopic examination of selected, representative, unweathered samples of Birmingham, Alabama, Silurian, sedimentary iron ores has fully revealed the nature of the phosphorous-bearing mineral grains. The grains are composed of carbonate-fluorapatite (collophane), range in size from 1 um to 2.25 mm, and exhibit varied types of intergrowth with hematite. Modal analyses conducted under cathodolumi-nescence have provided quantitative data on the a3undance of each of 15 types of phosphorous-bearing mineral grains and made it possible to assess the potential phosphorous liberation from four types of iron ore. The results indicate that 27% of the total phosphorous contained in the iron ores in the western part of the Birmingham district can be expected to be liberated by fine grinding; 60% for ores in the eastern part of the district.

Jan 1, 1982

By Gus Van Weert

Solvent extraction of iron from zinc refinery liquors has been investigated before, mainly on the MEHPA / HC1 stripping combination. Leakage of chloride into the zinc electrolyte and the costs of handling the ferric chloride eluate have prevented this option from being adopted. This work explores the stripping of the ferric loaded organic phase with nitric acid to take advantage of the possibility of regenerating up to 6N nitric acid, and clean spheroidal hematite production by autoclave treatment of ferric nitrate solution. The work was carried out with DEHPA (di 2-ethyl-hexyl phosphoric acid) in kerosine. Degradation testing proved the DEHPA to be very stable, when exposed to nitric acid solutions up to 6N and temperatures up to 70" C over a period of five days. Ferric iron was removed completely froma synthetic hot acid leach liquor, irrespective of the DEHPA concentration. Stripping the ferric turned out to be the problematic step. Although the stripping efficiency was considerable better at 50 than at 20° C, it decreased with increasing DEHPA/Fe ration in the organic phase. Eluates of no more than 5-10 g/l ferric nitrate were produced. surprisingly, nitric acid was found to be a less efficient stripping agent than sulphuric at equivalent normality and its efficacy levelled off above 4N. It was concluded that DEHPA does not appear to be the S.X. reagent to take advantage of the low cost autoclave decomposition of ferric nitrate opportunity in zinc hydrometallurgy and that another S.X. reagent, also resistant to nitric acid, but based on weaker compound formation is needed.

Jan 1, 1998

By Nieves Iglesias

The removal of the refractoriness of a gold bearing pyrite- arsenopyrite ore is studied. Flotation concentrates were prepared and leached with a dilute acidic ferric sulfate solution. The elemental sulfur film which forms on arsenopyrite in the oxidation process is not responsible for the low rate of the arsenic dissolution observed. A positive effect on the leaching rate is observed when Ag&apos; is added. This pretreatment eliminates the refractory nature of concentrates.

Jan 1, 1993

By Kimio Itagaki

The distribution behaviours of the VA elements between the gas, slag and matte phases in copper smelting were evaluated on the basis of the thermodynamic data, most of which were determined by the authors. The distribution is basically dependent on the process factors such as temperature, the content of the element in charge, the amount of the waste gas and degree of vapour saturation with the elements. The thermodynamic quantities such as the activity coefficients of the VA elements in matte, the activities of iron and copper, SO2 or 02 potential and the distribution ratio of the elements between the slag and matte phases seriously affect the distribution, and the behaviours in various smelters could be explained systematically and reasonably by considering the changes in these quantities, In oxidation smelting at PSO2= 0.1 to 1 atm, the proportion of arsenic and bismuth in gas is predomi22t for the arsenic and bismuth distributions in both smelting and converting stages. The degree of vapour saturation has serious effect on the distribution, and sufficient contact between gas and matte phases is desirable for transferring arsenic and bismuth into gas phase.The elimination of antimony by means of vaporization is not significant. In reduction smelting at po2 = 10-11 atm, the proportions of arsenic and antimony in the gas phase are quite small, but the proportion of bismuth does not change significantly.

Jan 1, 1983

By Paul E. Queneau

The QS (Queneau-Schuhmann) copper converter is a gently sloped, stepped, horizontal kiln-type tilting reactor in which desired bath oxygen activity, compositional and temperature gradients are created by countercurrent flow of matte and slag phases through a series of controlled bubble plume, mixer-settler configurations. Flow of gas and slag is normally concurrent. Copper sulfide concentrates are top-fed, employing oxygen flash burners. Oxygen and oxygen-carbonaceous fuel mixtures are bottom-blown into the smelting bath through judiciously located, independently regulated submerged injectors. Composition and mass flow rates of injector inputs are controlled to produce bubble plumes of desired character, without jetting through and out of the bath. The mixer-settler pattern can be reinforced if desired by employment of suspended shallow baffles. State-of-the-art instrumentation provides timely information required to govern key process variables. The outstanding capabilities of the QS converter for coppermaking have now been indicated by the current success of industrial QSL (Queneau-Schuhmann-Lurgi) leadmaking reactors. Modified converter designs are employed for leadmaking, nickelmaking and steelmaking.

Jan 1, 1993

By A. A. Bustos

A model was developed to simulate the blow-by-blow operation of the converting process. From the weights, compositions and temperatures of all converter feeds the model calculates the composition and tonnage of both converter matte and slag as well as bath temperature at the end of each blow. The development of the model and its application to the converter aisle operation are described. There is good agreement between model predictions and observed results. At the present time the model is being used to investigate different converting schemes and their effect on pay metal recoveries, slag chemistry and temperature of the bath. Future work involves the use of the simulation model as a process control tool for the converting operation.

Jan 1, 1988

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 Michael B. Mooiman, David J. Kinneberg, Philippe Cettou, Leo W. Simpson, Pierre Ramoni

"The demand for high purity precious metals began with certain industrial applications having uncompromising requirements for quality and performance. As industrial uses proliferated and as the jewelry industry became increasingly sophisticated, the demand for high purity gold has reached the point where 99.99% is now the standard in the marketplace. A similar evolution is expected for other precious metals.In this paper, we examine both the production and use of high purity precious metals, specifically gold, silver, platinum and palladium. After defining what is meant by ""high purity"", we discuss the various analytical techniques used for measuring impurity concentrations. Next, we review process strategies employed by extractive metallurgists to produce high purity precious metals. Lastly, we describe some of the principal applications for high purity materials including thick films, thin films, bonding wire, thermocouples and jewelry manufacture.Precious metals have unique physical properties that, despite their expense (and the ever-continuing search for more economical alternatives), make substitution difficult if not impossible. These physical properties are dramatically affected by small concentrations of certain impurities. As long as manufacturers continue to demand quality and performance, there will be a need for high purity precious metals.IntroductionIn the precious metals industry, the qualifier ""high purity"" describes any specification over and above commodity grade. High purity specifications delineate lower limits on overall metal purity or upper limits on individual impurities or both. Sometimes, if these special requirements become commonplace, either because of improved refining technology or because of market pressures, yesterday's ""high purity"" material becomes tomorrow's commodity. This transition is now occurring with gold bullion and probably will soon occur with platinum and palladium as industrial use of these materials grows."

Jan 1, 1998