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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 Richard D. Hangi

Process mineralogy techniques are uniquely applicable to industrial problems related to the extractive metallurgy of nickel, cobalt, and associated metals. Reflected 1ight microscopy, together with selected determinations by scanning electron microscopy-energy dispersive spectrographic analysis and electron probe microanalysis, provides the means to identify the ore minerals cobalt and nickel ores, determine the abundance of each ore mineral, assess the extent of intergrowth between the cobalt and nickel minerals and other ore and gangue minerals in the ores and concentrates, and predict the potential success of cobalt and nickel extraction by grinding, flotation, pyrometallurgical, and hydrometallurgical treatments. In addition, the extent of locking of the cobalt and nickel minerals with each other and with the gangue minerals can be directly observed by reflected light microscopy. Where ores have been treated by hydrometallurgical procedures, reflected light microscopy can serve to determine the causes of excessive leach consumption. Finally, the partitioning of cobalt and nickel between high-temperature synthetic phases produced by pyrometallurgical treatment can be precisely determined by process mineralogy techniques. Case histories from cobalt and nickel deposits illustrate the value of applied mineralogical techniques in the study of cobalt and nickel ores, beneficiation, hydrometallurgial, and pyrometallurgical products.

Jan 1, 1993

By W. G. Davenport

The offgas from flash furnaces inadvertently contains dust. The dust contains 25 to 30% Cu so it must be treated for Cu recovery. This is almost always done by recycling it back through the flash furnace*. This chapter shows how dust production/recycle is included in our matrix calculations. It then discusses the effects of dust production/recycle on flash furnace industrial oxygen and oil requirements. It concludes that re-smelting of dust requires considerable industrial oxygen and fuel, so that dust production should be minimized. Recycled dust also takes the place of new concentrate in the flash furnace feed system, decreasing Smelter productivity -another reason to minimize dust production. Compositions of industrial dusts are given in Appendix VII and Table 18.3. Industrial quantities are given in Tables 2.1, 3.1, 19.1,20.1' and Appendix VI.

Jan 1, 2001

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 K. Krishnapisharody, G. A. Irons

"The modeling of gas-liquid plumes in steelmaking ladles has been the subject of many investigations. In most studies, the “modified” Froude number, based on the momentum of the injected gas, has been employed to characterize two-phase plumes. This approach has several shortcomings and is critically reviewed in the present work. Based on an extensive review of previous work and theoretical considerations, it is demonstrated that the injected momentum and consequently, the modified Froude number has no significance to gas blowing operations in Ladle Metallurgy. Instead, an approach based on the “plume” Froude number, previously shown by the authors as the proper form for Froude similarity, is extended as a simpler alternative.IntroductionGas injection is central to most Ladle Metallurgy operations. During ladle processing, the steel melt is usually stirred by an inert gas like Argon through porous plug(s) fitted in the bottom of the ladle or a lance inserted deep into the melt. The purging serves several purposes viz., homogenizing the melt, flotation of inclusions, enhancing the rates both of refining reactions and dissolution of alloying elements and promoting inter-phase interactions in the ladle.The topic of gas injection into liquid baths has been the subject of several investigations in the past. A great deal of this work, both experimental and computational, was devoted to describing the structure and properties of two-phase plumes as reviewed recently [1]. Generally, the ascending two-phase mixture is sub-divided into three distinct regions [2]: the jet core, transition and the bubble plume, respectively. The jet region, where the momentum of the injected gas is transferred to the bulk liquid, is also called the ‘momentum region’. In a similar manner, the plume is called the ‘buoyancy region’ where the motion of liquid is caused by the buoyancy force exerted by the bubbles. The proper characterization of these regions is important for the analysis and modeling of stirring operations in Ladle Metallurgy. Although many mathematical correlations exist for this purpose, some issues of theoretical and practical interest to the modeling of gas-liquid plumes need further attention."

Jan 1, 2012

By George E. Cook, Peter C. Levick, Francis M. Wells

"Relationships are established between the peak current of a pulsed, rectangular current waveform and the pulse current duty cycle under conditions of constant arc power. By appropriate choice of these interrelated parameters, it is shown that the arc pressure may be varied over a wide range even though the arc power is held constant. The methodology is suggested as a means of countering the effect of gravity in 5-G welding, while maintaining constant heat input to the weld. Combined with appropriate penetration sensors, the methodology is additionally suggested as a means of controlling penetration. IntroductionBoth low frequency pulsation (typically 0.1 - 20 Hz) and high frequency pulsation (> 100 Hz) are often used with GTA welding. Benefits derived from pulsing include improved weld quality and better process control.Advantages cited for low frequency pulsation include claims that the total heat input to the weld is reduced, the weld bead size is reduced, weld penetration is increased, grain size is reduced, porosity is reduced, weld distortion is reduced, thinner materials can be welded successfully, and the tolerance of the welding process to material and production variations is improved (1-16). With respect to the latter, pulsing aids control of weld bead penetration by increasing the tolerance to component dimensions and joint fit-up. It also reduces the sensitivity to disparities in heat sink, and it helps to reduce distortion in thin section material or distortion attributable to poor clamping. In certain materials it can reduce the sensitivity to surface oxides and to cast to cast compositional variations (16). Low frequency pulsation is also useful in welding thick materials mated by a prepared groove. In these applications the low frequency pulsation is used to obtain proper sidewall fusion as the tungsten electrode is weaved from one side of the groove to the other. In this case the weld current pulsation is synchronized with the cross seam weave pattern, such that the high current pulses occur at each sidewall. This type of low frequency pulsation has proven particularly useful in welding with narrow width groove designs (17-21). Finally, Ecer (22) has shown that the pulsed current arc is more stable against magnetic disturbances than an equivalent constant current arc."

Jan 1, 1986

By D. McConchie

Management of caustic red mud wastes at the QAL bauxite refinery uses an innovative approach . involving neutralising the red mud with seawater; solids settle in a Red Mud Dam and residual water (pH = 8.6) is discharged to a tidal inlet. A survey of 18 trace elements in sediment, water, mangroves and molluscs, and an ecological survey of benthic fauna in the inlet, and at near-pristine control sites, revealed no significant trends that were linked to the discharge, except for the concentration of Al which was slightly elevated within 100m of the outfall. Trace element concentrations in water samples were close to, or below, world average seawater values and oysters collected near the outfall were acceptable for human consumption. The impact of discharges is minimised by a high tidal range, >60% flushing of the inlet in each tidal cycle, and the very high trace element binding capacity of sediment in the dam (> 100meq/ 100g dry mud).

Jan 1, 1996

By Gavin K. W. Freeman

The efficient separation of cobalt from nickel is a fundamental objective in the refining of cobalt. Based on recent experience at the Corefco refinery in Fort Saskatchewan, the identification of a novel process for the selective precipitation of cobalt from aqueous ammonia leach liquors is described. The addition of calcium sulphate, CaSO4.2H2O (gypsum), to an aqueous solution containing cobalt(III) hexammine sulphate, [Co(NH3)6]2(SO4)3, will result in the precipitation of a sparingly soluble double salt having the stoichiometry, [Co(NH3)6]2(SO4)3.2CaSO4.xH2O, where x = 4 or 6. Leach residues, which may contain a significant quantity of cobalt associated with the cobalt calcium double salt, can be washed with process solutions that contain ammonium carbonate. After contact with ammonium carbonate, the cobalt is recovered into solution, while the calcium is re-precipitated as the insoluble carbonate. The simplicity of this elemental separation and its high selectivity for cobalt, as well as the demonstrated usefulness in improving cobalt recoveries, are the basis for the potential applications of this process.

Jan 1, 2003

By Rick Honaker

Rare earth elements (REEs) contained in coal and associated mineral matter exist in several forms including micro-dispersed minerals, ion adsorption onto clay surfaces, and chemically bound. Tests found that REEs can be effectively recovered from certain components of three coal sources by leaching under mild conditions followed by solvent extraction. A range of pH values were evaluated at solution temperatures of 25 and 75 °C. When using 1.2 M of sulfuric acid, nearly 85% recovery of the REEs was extracted from the middlings material collected from an operating plant. Acid leaching of a second middling source from another plant resulted in 60% of the total REEs being recovered under the same leaching conditions. Solvent extraction treatment of the leachate produced from six different coal sources resulted in products containing up to 50% total REEs from feedstocks starting with around 300 ppm.

By Asmo Vartiainen

Background of Direct-to-Blister Flash Smelting is discussed; especially slag chemistry relating to copper solubility, slag fluidity and impurity behavior. In December, 2000, Mini-pilot Flash Smelting test runs were carried out at Outokumpu Research Oy to produce blister copper from Chilean concentrate and white metal and from a mixture of them. Tested slag types were iron silicate slag, ferrous calcium silicate slag and calcium ferrite slag with different slag compositions and different concentrate/white metal ratios. The test runs were successful. The fluxing effect of copper oxide was clearly demonstrated and ferrous calcium silicate slags remained fluid on a very wide liquidus range. The distribution of arsenic between ferrous calcium silicate slag and blister copper is much higher than between iron silicate slag and blister copper. This successful test run with the new slag type offer new possibilities in Direct- to-Blister process design.

Jan 1, 2003

By R. Boom, B. Kraaijveld, H. Kuntzel, Y. Meteleva-Fischer

"Alloying refining with rare earth elements followed by acid leaching was examined for the potential of upgrading of metallurgical grade silicon. Microstructure study of silicon alloyed with small additions of rare earths showed behavior relatively similar to the influence of calcium addition. After alloying with neodymium the phosphorus content was detected in various intermetallic silicides containing neodymium and iron. The content of lanthanum and neodymium in refined silicon was by several times lower than that of aluminium and calcium. Alloying with lanthanum and neodymium at smaller additions than calcium reduced the phosphorus content down to the same level. The efficiency of lanthanum and neodymium in removal of boron and phosphorus at the 1-2 wt% of their additions and their low solubility in silicon make the alloying with these metals followed by acid leaching an attractive option for the refining route of metallurgical grade silicon up to solar grade.IntroductionA striving for a cheap ""green"" energy directs the research interests in silicon solar cells towards new efficient refining routes for metallurgical grade silicon (MG-Si, -98% purity). The silicon price determines up to high extent the solar module's price, so that cheap and efficient metallurgical process is awaited. The research challenge is to fulfil the purity requirements of solar grade silicon (SoG-Si, 6N) by competing with the energy-consuming and environmentally unfriendly Siemens process. Most difficult impurities to remove are boron and phosphorus, so technologies dedicated to their efficient removal attract an attention of industry and academia.Alloying refining (also known as solvent refining) is one of the most promising refining options, which is based on a principle of solid-liquid extraction using limited solubility of impurity elements in solid silicon [ 1]. Various elements were proposed for alloying refining: aluminium [2], calcium [3], tin [4], iron [5], copper [6] etc. The attractiveness of the alloying refining is in decreasing a melting point of the metal mixture and an affinity of the alloying element to the most harmful impurities, especially to boron and phosphorus. However, the difficulties are still faced due to self-solubility of the alloying elements, their low affinity to boron and/or phosphorus, silicon losses and necessity of removal of the silicide impurity phases in an additional step, using acid leaching [7], fractional melting [ 8] etc."

Jan 1, 2013

By Ivan Imris

The common problem of new and conventional technology of copper production is the copper losses in the slags, which may be divided into mechanical and physico-chemical losses. In the first group can be included particles of mechanically entrained or floated unsedimented matte particles which coexist with slag. On the other hand, the physico-chemical losses are caused by solubility of copper in the slag in the form of sulphide and oxide. The copper losses in the slags from different processes has been predicted by calculation from thermodynamic data and compared with those determined by microscopic examination and quantitative electron microprobe analysis. Depending on the forms of copper losses in the slag the reduction of copper losses in the slag or the slag cleaning process could be suggested.

Jan 1, 2003

By Varadarajan Seshadri

A physical model based on similarity principles was constructed for simulating the RH degasser of CST (Companhia Siderurgica Tubarao, Vitoria, ES, Brazil) to evaluate the circulation rate of the metal which essentially defines the degree of exposure of the metal to vacuum in the chamber and thus of the refining rate, The circulation rate on the other hand will influence the decarburization rate and removal of dissolved gases like nitrogen and hence it is essential to optimise this parameter to get maximum refining efficiency with minimum refining times, thus improving the productivity of the secondary refining process. Mixing characteristics in the ladle is evaluated by pulse tracer addition using conductivity-meters located at the down leg as well as at several locations in the ladle. The influence of gas injection through nozzles in the upleg with simultaneous bottom injection of gas as well as nozzle blockage on the circulation rates were investigated. Also simulation experiments of kinetics of decarburization were carried out using CO2 adsorption-desorption process in sodium hydroxide solution as circulating fluid and the effect of, bottom gas flow rate in this case was also evaluated. The results were carried over to prototype and to optimize the process.

Jan 1, 2003

By Muhammad A. Imam, Ramana G. Reddy

This study provides a reasonable evaluation of the Mg-B binary system. Magnesium and Boron (Mg-B) alloys were investigated to determine their thermodynamic properties employing solid state electrochemical cells based on CaF2 electrolyte represented as –Pt; Ar= MgþCaMgF4 f gCaF2 k kf½Mg B alloy þ CaMgF4 g=Ar; Pt+ Investigations were performed over the temperature range of 773–873 K to measure the electromotive force (EMF), which was used to derive the partial Gibbs Free energies of the alloys in the composition range of XB = 0.07 to 0.95. The activities of Mg were also calculated from partial Gibbs Free energies. The activities of Mg in MgB2, MgB4, and MgB7 were expressed as a function of temperature respectively, ln aMg = 4.27–9.32 × 103/T, ln aMg = −7.54 + 6.67×103/T, and ln aMg = 4.93–19.57 × 103/T, where T is the temperature in K. From this expression, the activity of Mg for these intermediate phases can be extrapolated at a higher temperature to get the accurate phase boundaries for the Mg-B system.

Mar 1, 2017

By Shaohua Ju, Feng Jiang, Chuanhua Li, Jinhui Peng, Libo Zhang

A T-junction microchannel is proposed to overcome the existing problems in conventional solvent extraction of indium from zinc hydrometallurgical process. Experiments were performed to separate In3+, Fe3+ and Zn2+ from sulfate solutions using Di-(2-ethylhexyl)phosphoric acid (D2EHPA) as the extractant. The effect of parameters such as pH, microchannel size and contact time on the extraction behavior of In3+, Fe3+ and Zn2+ was investigated. At contact time of 2.52 s and initial solution pH of 0.48, the extraction efficiency of In3+, Fe3+ and Zn2+ was 99.13%, 8.31% and 2.45%, respectively and separation factor of In3+/Fe3+ and In3+/Zn2+ were almost 1229.54 and 4864.98, respectively. Then, the loaded organic phase was stripped in T-junction microchannel. At contact time of 33.6 s, 99.64% of stripping efficiency of In3+ and stripping equilibrium were reached, while concentration of Fe3+ and Zn2+ was lower than 0.01 g/L with good separation of In3+ from Fe3+ and Zn2+.

Jan 1, 2016

By Larry Southwick

This Peirce-Smith Converting Centennial symposium is celebrating the contributions of two men, William Peirce and E.A.C. Smith, in advancing technology allowing the copper industry to realize its full potential. However, theirs is representative of a larger story: New, simpler technology releasing the stranglehold of older, more complicated technology, new developments in vessel configuration and design finding alternate routes around dead ends in operability, advances in technique and concepts removing roadblocks of cycle time and capacity, and overall innovation opening up vast new reserves around the world to those companies willing to embrace those improvements. Our story is also one of personalities, stubborn smeltermen versus the innovators, those inside the industry versus those from outside. It is a story of an initial borrowing from the steel industry, but also Peirce and Smith, from the refining end of the copper business, taking the ideas of Baggaley from Pittsburgh’s steel and airbrake industry, who built on what Hollway, Manhès and David, Douglas, and others had done in smelter tests, further to compete with the previous primacy and closely held expertise of the copper smeltermen in Wales. These advances have been well recorded in photographs taken over the last 150 years. A number were submitted especially for this symposium. Many others were published in the mining and metallurgy press of the times. Several mining schools also retained copies of photos either taken during field trips, or donated to the school by alumni and operating companies. This presentation will provide a selection and discussion from these sources of “converters in action”, describing the various designs, operations and developments depicted. The focus here will be on the first roughly 60 years of copper converter development, from Bessemer’s days at the dawn of this new idea, up to and slightly past the time of initial adoption of Peirce and Smith’s designs.

Jan 1, 2009

By R. L. Nyirenda

One of the problems with ammoniacal-ammonium carbonate leaching of EAF carbon steelmaking flue dust is that zinc present in spinel phases is not leached. This paper presents results of test work in which prior to leaching, EAF dust was reduced with CO containing gas to decompose the spinels into zinc oxide and iron bearing phases, mainly metallic iron and wustite. From such reduction products, the amount of zinc leached increases but the iron co-leached becomes extensive. The effect of various leaching parameters such as liquor concentration and redox potential on zinc and iron dissolution has been investigated. Supplementary experiments utilizing pure zinc oxide and pure iron phases were also carried out. Results show that the co-dissolution of iron from severely reduced EAF dust cannot be prevented. This is because the wustite phase contains zinc which can only be leached when iron also dissolves. Further, the zinc bearing wustite phase is not totally soluble so that the residue cannot be made zinc free. In the absence of air, dissolution of metallic iron hardly occurred, though in leaching experiments of a long duration its transformation to a spinel structure was observed.

Jan 1, 1992

By K. Murayama, M. Kawakami, T. Takenaka, S. Yokoyama

"Cokes play an important role of spacer in blast furnace. However, they degenerate during Boudouard reaction. Blast furnace cokes are reacted with pure C02 at I 072 to 1673 K. Reaction rate was obtained by the weight change of spherical specimen. The specimen after reaction was examined by microscopic observation. The reaction rate increased with temperature and was expressed by two Arrhenius type lines. The activation energy was 126 KJ/mol at higher temperature than 13 73 K and 202 KJ/mol at lower temperature range. At the higher temperature range, the reaction proceeded from the surface leaving unreacted core, whereas homogeneously whole inside at lower temperature. The porosity increased from the center to surface at higher temperature, whereas it was almost constant at lower temperature.IntroductionThe cokes have the function of fuel, reductant and spacer to keep gas and liquid flow in the blast furnace. Thus, the reaction mechanism of coke with several gas and the strength after the reaction should be important factor to control the blast furnace operation. The reaction mechanism of coke with C02 has been studied extensively. The rate equations were derived by Gadsby[ I], Ergun[2] and Turkdogan and Vinters[3]. They were compared and discussed by Kobayashi and Omori [ 4]. Effect of crystallization degree on the reaction rate was examined by Kashiwaya and Ishii[5]. Catalytic enhancement effect of ash componets have been clarified by Kashiwaya et. al. [6]. Although degradation of coke in blast furnace has been examined recently[7], however, the degradation of coke after the reaction with C02 has not been well clarified yet. In the present work, the metallurgical coke specimen was heated in N2 and C02 and the reaction mechanism and degradation behavior after the reaction was investigated."

Jan 1, 2000

By P. Henry

A novel electrochemical cell has been developed for the recovery of MnO2 from residue of pyrolusite ore leading loaded with Fe, Al Ni, Co and Si impurities, This new process can be considered as an alternative to the traditional methods : S02, H2O2 or bioleaching. It has been observed to proceed fairly rapidly and could prove to be a more economically viable process, as well as being more environmentally acceptable. Electrochemical characterization and kinetic studies have shown that MnO2 is effectively leached by electrogenerated ferrous ions at high current density from a pulp containing less than 5 g8 Fe. The chemical reactions are : Cathode (inox) : 2F23+ + 2e ? 2 Fe2+ Bulk: MnO2 + 2 fe2+ 4H+ ? Mn2+ + 2 Fe3+ + 2 H2O Anode (Pb-Ag) : H2O ? ½ O2 + 2H+ + 2e Global: MnO2 +2H+ Fe2+ = Mn2+ + H2O + 1/2 O2 The catholyte (MnO2 pulp) circulates upward in the expanded mesh cathode separated from the sulfuric acid solution anolyte by a separator which shows high mechanical resistance, low porosity, low potential drop, and reasonable cost. Laboratory and mini-pilot tests have led to the construction of an OT crating pilot plant (100 kg/hr) able to leach more than 95% of Mn, Ni, Co at 1000-1200 A/m2, 50°C with high faradic yield (> 95 %) and low power consumption (3.2 kWh/kg kWh/kg &4D). New applications like the treatment of spent Zn-Mn batteries, polluted soils, spent catalysts and oxide ore (cobalt, nickel) with electrogenerated redox species are now investigated at a laboratory and mini-pilot scale.

Jan 1, 2000

By Ray Y. Lin

This study explores the formation of sodium pyrosulfate in molten sodium sulfate resulting from dissolution of SO3 at temperatures between 1160 and 1250 K. Solubility of SO3 in Na2SO4 melts at temperatures between 1160 and 1250 K under gas mixtures of SO2, O2 and argon was investigated applying a thermogravemetric analysis (TGA) technique. The activity of Na2O in the melt was determined with a high temperature electrochemical cell (ECC). Results showed that the SO3 solubility in molten Na2SO4 increases with decreasing temperatures and increasing SO3 partial pressures. Enthalpy of SO3 dissolution in molten Na2SO4 was calculated to be -119 kJ/mol for infinite dilute solutions. Thermochemistry of Na2SO4-Na2S2O7 melts was analyzed based on information obtained from both TGA and ECC techniques. Detailed examinations of the earlier low temperature measurements in the Na2SO4-Na2S2O7 system along with data from this study reveal that the solution behavior between Na2SO4 and Na2S2O7 can be satisfactorily treated as regular with the interaction parameter, , being 2.7 kJ/mol. The phase diagram and the field of SO3 partial pressure has been generated with the thermodynamic calculation using a regular solution approach.

Jan 1, 2006