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By G. B. Harris

Much has been written over the past decade concerning the disposal of arsenic from metallurgical processes. In Canada, there are proposed regulations which would classify arsenic in the Primary Group of twenty one persistent, toxic pollutants to be banned or phased out. Since many nickel and cobalt ores, not to mention those of copper, gold and uranium, contain significant amounts of arsenic, it is pertinent to assess the current state-of-the-art of its disposal. The literature is reviewed, and it is demonstrated that from a purely chemical point of view, the family of ferric arsenates largely immobilize arsenic. There is clear evidence from laboratory studies that both crystalline ferric arsenate (scorodite) and amorphous ferric arsenates in which the molar Fe/As ratio is at least three (Fe/As = 3) have very low arsenic solubility; plant data are given to support this. The debate over the long term stability of these compounds continues however; the evidence presented for long term stability and for compound breakdown is critically reviewed in the light? of the recent structural studies, and the role of base metals in these compounds evaluated. Finally, conclusions are drawn as to the viability of a purely chemical process for the long term disposal of arsenic from metallurgical processes.

Jan 1, 1993

By M. G. King

In 1982, Asarco operated six smelters and refineries producing primary copper, lead, zinc, silver and gold. At that time Asarco was still reliant on its custom smelting and refining roots and mined only 25% of its smelting and refining capacity for copper and 10% of its lead smelting and refining capacity. By 1992, Asarco had been reshaped to become largely an integrated primary metal producer operating four smelters and three refineries. Zinc is no longer refined and the mining capacity has been increased to meet 100% of copper smelting and 50% of lead smelting needs. Only one custom smelter is in operation. This paper describes the metallurgical changes and challenges which have occurred in this restructuring of Asarco's operations while maintaining Asarco's position as one of the largest non-ferrous metals producers in the world.

Jan 1, 1993

By D. de la Villa

From 1989 to 1992 Rio Tinto Minera has developed and implemented a productivity program in its Huelva Plant, including Smelter, Acid Plant and Electrorefinery. This Plan was designed in order to increase productivity, reduce emissions and produce a better quality of cathodes. This paper describes investments and operating improvements involved in this project, focusing on Smelter and Acid Plants, and comments the results obtained so far.

Jan 1, 1993

By C. W. Won

a-etchant solution is the waste material obtained during the etching by ammoniacal solution of printed circuits for PCs. This material contains a substantial amount of copper (13-14%) but is usually discarded after neutralization. In this work, copper recovery from such solutions by electrowinning or cementation using iron scrap was tested. For each method, the effects of temperature, solution pH, initial copper-ion concentration, and reaction time were investigated to obtain optimal conditions for copper recovery.

Jan 1, 1993

By B. Q. Li

A numerical study of the developing fluid flow and thermal aspects during the staning phase of aluminum continuous casting processes is presented. The deforming finite element method, coupled with a quasi-Lagrangian formulation, is used to represent the growth of an ingot and the dynamic fluid flow and thermal behavior that evolves in the growing ingot. The mathematical formulation of the problem and the numerical treatment are discussed. The algorithm solves the free moving nodes as part of total unknowns with an automatic time step control for time integration. This permits an optimal computing efficiency while still keeping the computational errors under control. A selection of the results obtained using the algorithm is presented. The results are concerned with the evolution of fluid flow, temperature and solidification phenomena during a DC round ingot casting process, as it evolves from the beginning of casting operation to a steady state. These results show that the time-varying, complex fluid flow and thermal phenomena during continuous casting processes can be very well represented by the computational algorithm. The results also illustrate that, during the casting process, ~e fluid flow and temperature fields change drastically at the initial stage but evolve slowly afterwards

Jan 1, 1993

By S. Yuan

Oxygen ion conducting yttria-stabilized zirconia (YSZ) tube was used to remove oxygen from molten Cu at 1373K. Outer surface of the tube was in contact with the melt and the inner surface containing a thin layer of porous Ni-ZrO2 cermet electrode was in contact with a reducing gas. The migration of oxygen species (O2-) from the Cu melt through the YSZ tube is accompanied by an equal and opposite flux of electrons maintaining electroneutrality. Without applying an external EMF, the fluxes are maximized by short circuiting the melt with the cermet electrode. For efficient oxygen removal, the YSZ tube must be thin, contact resistances should be negligible, and the electrodes must be porous and cover the entire electrolyte surface for charge transfer. This refining process is environmentally sound, can use reducing gases such as H2, CH4 and CO without running the risk of increasing H or C content of the melt.

Jan 1, 1993

By Animesh Jha

Univariant diagrams are constructed for the reduction of nickel and cobalt oxide and sulphide minerals. The results from the carbothermic and hydrogen reduction of sulphide minerals are compared. The importance role of lime and calcium sulphate in controlling the emission of sulphurous- gases during reduction reaction is also explained. The mechanism of carbothermic reduction of nickel sulphide is explained by examining the sulphur exchange and reduction reactions. The phase equilibrium relationships that determine the formation of multicomponent liquid are characterised. Also the governing equilibria for inert atmosphere calcination- roasting of nickel and cobalt sulphide minerals are also described for the metallization of nickel and cobalt.

Jan 1, 1993

By Stavros A. Argyropoulos

Exothermic mass transfer takes place in various areas involving metallic systems, ranging from liquid metal processing operations to the growth of thin films in microelectronics. The formation of intermetallic compounds plays an important role in the exothermic mass transfer of metallic systems. Two types of exothermicity are identified , namely , Microexothermicity and Macroexothermicity. The former is encountered when small amounts of metals are mixed, while the latter is exhibited when a solid metal in a lump form is added into liquid metal. In this paper two types of exothermic mass transfer in metallic systems will be presented and reviewed. Mathematical modelling work for these types of exothermic mass transfer will be analyzed.

Jan 1, 1993

By Tom W. Gonzales

Magma Metals Company commissioned a 3000 tpd Outokumpu flash smelting furnace in July 1988. Through September 1992 the PSP has smelted a first campaign record 4.1 million tons of concentrate. This paper discusses modifications made to the original process equipment to overcome design flaws as well as future design changes currently under consideration.

Jan 1, 1993

By Andres Vikdahl

The Rönnsktär smelter has recently undergone a series of technical and operational changes. This changes are caused by our own will to remain and gain in competivety and to adapt to the ever changing surroundings. To be able to remain competitive in surrounding with high wage costs, high inflation and high environmental standards thorough cost management is needed. The Swedish economic policy in the beginning of the 80'ies consisted amongst other things of two devaluations. The exchange rate of the Swedish Krona was reduced with approximatively 25 %. This boosted the profits of our export industry, some even believed we entered the land of milk and honey ... And working in this promised land where everything turns into profit it is very difficult to be careful and restrictive with your spendings. Apart from some healthy and fruitful investments we allowed ourselves yearly steady increases in salary for ever reduced number of worked hours and we of course employed more people. Inflation rates went up and so did property prices. In 1986 finally reality catched up on us. Reality in the form of too high costs started to hit Swedish export industry 5-6 years after the big devaluations. Furthermore the high inflation rate also hit the domestic industry a couple of years later. Together with other important factors Sweden faced a severe home-made recession in the beginning of the 90'ies. With this background we now report and analyse our smelter's performance and operating results, shown in fig 1 The main constrictions on smelting and refining at Rönnsktär are today: * Income restrictions by governmental production level Limit * Throughput resmctions by governmental emission limit * High capital costs in the aftermath of Swedish high inflation in the recent decade * Low work force turnover Below we will illustrate how we tackled with these issues along the following lines: * People * Quality * Technology

Jan 1, 1993

By Y. Y. Sheng

Plume flows created by gas injection into liquid metals have been studied extensively, however the dynamics of bubbles within the plume have not received adequate attention, particularly for large, irregular bubbles, characteristic of the processing of liquid metals. The present model uses a combined Eulerian-Lagrangian approach in which an estimated void fraction distribution is used to calculate the liquid flow field with a conventional Eulerian scheme. The trajectories of bubbles are then computed in a Lagrangian manner using the estimated flow field, and experimentally measured information on bubble drag coefficients', lateral migration due to lateral lift forces and interaction with turbulent eddies, and variation in bubble size due to break-up. Turbulence in the two-phase zone is modeled with a modified k-e model with extra source terms to account for the second phase which have been recently determined by the present authors. The computed void fraction and turbulent liquid flow field distributions are in good agreement with experimental measurements.

Jan 1, 1993

By Jerold L. Johnson

Remediation of small-arms firing ranges is being investigated by the Naval Civil Engineering Laboratory and the U.S. Bureau of Mines. Scheduled closures of military installations, as well as the management of active ranges, require the development of methodologies for heavy metals removal to prevent their entering the surrounding environment. The impact berms contain high concentrations of metals, and the soil and vegetation surrounding the berms were found to have slightly elevated levels. The heavy metals characterized are in the form of whole bullets, a wide size distribution of free fragments, smeared lead on the surface of the soil grains, and very finely attached particles. Gravity beneficiation can remove liberated metal contamination effectively. Weak acetic acid leaching shows promise in lowering the final metal contamination to allow the ,soil to pass the Environmental Protection Agency's (EPA) Toxicity Characteristic Leaching Procedure (TCLP) criteria.

Jan 1, 1993

By Willem P. C. Duyvesteyn

A novel hydrometallurgical process for Escondida copper concentrates has been developed by The Minerals Laboratory of BHP. The Escondida Process consists of concentrate leaching, solution purification, electrowinning and residue flotation. Part of the copper will be sold as high grade concentrate and part as high purity SX-EW copper. Contrary to previous efforts for the development of a hydrometallurgical process for copper concentrates, this patented process does not advocate the total dissolution of copper. It only aims for the copper that is readily soluble in a mildly oxidizing environment with an ammoniacal or acidic lixiviant. Both lixiviants were studied, but ammonia was preferred because of fast kinetics at ambient temperatures and pressures. By controlling the oxidation potential, the formation of sulfate ions and, consequently, of an ammonium sulfate byproduct, is precluded. These mild leaching conditions also prevent the dissolution of unwanted impurities and result in the production of ultra-high purity electrowon copper. Solution purification is carried out by solvent extraction with LIX-54. The very high loading capacity of this organic results in a compact SX circuit, consisting of two loading, one scrubbing, and one stripping stage. As the organic is selective for simple copper ions, the copper amine complex is broken down and free ammonia is regenerated and recycled for leaching. High purity copper cathodes are produced in a conventional sulfuric acid based electrowinning system. One scrubbing step is needed to separate the ammoniacal circuit from the acid circuit. Limiting copper dissolution to less than 50% also provides an opportunity to produce high grade concentrates by residue flotation. Copper recoveries in excess of 98% with precious metal values reporting to the final concentrate can readily be obtained. Complete breakdown of the copper mineral- pyrite middlings results in a final concentrate grade that can be even higher than the original feed material. The Escondida Process also provides an opportunity to accept lower grade copper concentrates producing improved copper recoveries in the mill and yet high quality concentrates for marketing. The Paul E. Queoeau International

Jan 1, 1993

By F. Shen

Qualitative and quantitative results obtained during the physical modeling of the molten aluminum flow in a tundish using an aqueous system are presented. Surface tuft, free-surface powder and laser sheet visualization techniques were utilized for qualitative studies, whereas laser Doppler velocimetry was used to elucidate the 3-D flow regimes quantitatively. The results of the study are used for validation of the CFD codes, and to explore the effect of the alterations below the nozzle in order to: (1) decrease turbulence levels, and (2) collect the inclusions. Near the nozzle, the interaction of the impinging jet and the inclined walls gives rise to vortex structures. Downstream of the nozzle, two counter-rotating secondary cells diminish in strength. As flow turns through the bend, a separation region is created. The flow heading into the closed duct is seen to be nonsymmetric. A video tape highlighting the major findings is presented.

Jan 1, 1993

By Mariana H. Staia

Thermodynamic calculations based on the free energy minimization method were performed for the system Ti-Fe-Mn-0-C1-C in order to evaluate the chemistry associated with the chlorination of an ilmenitic concentrate using CCl4. In the calculations various weight ratios of FeTi03/ CC14, a , were considered, which varied between 0.32 to 0.98 at temperatures ranging from 673 K to 1273 K , at atmospheric pressure. The results obtained indicated that the operating conditions for a process in a packed bed reactor, which implies the chlorination of both Fe and Ti, are 0.39 < a < .49 at T 1173 K.

Jan 1, 1993

By Jun Li

Several metal sulfides were examined in-situ by Raman spectroscopy before and after anodic oxidation. Results obtained for chalcocite, chalcopyrite, covellite, galena, pyrrhotite and pyrite electrodes are presented. Under appropriate conditions, sulfur was detected after a potential was applied to the mineral electrodes for a threshold period of time. For all the minerals, application of a negative potential on the oxidized mineral reduced the surface product and the sulfur peaks disappeared from the observed spectra. For those minerals containing sulfur as S< in the crystal lattice, polysulfides were identified as oxidation intennediates.

Jan 1, 1993

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 Seshadri Seetharuman

The present paper summarises a series of measurements of the interaction parameter of oxygen in liquid copper with respect to a third element, e(M)o, where M is Mn, Zn, As, Se or Te which are common impurities in the liquid metal. The technique employed was the solid electrolyte galvanic cell method. The cell used may be represented as Pt, W or cermet / Cu-O-M // ZrO2 - CaO // AO, A /PT where AO/A represents a suitable oxide/metal reference. The measurements indicate that Mn and Zn interact very strongly with oxygen in liquid copper while, in the case of arsenic the interaction parameter is nearly zero. The behaviour of the elements Se and Te is unique with respect to oxygen interactions in copper bath. At oxygen levels, xo= 10-4 ? 10-5, the apparent interaction parameters are negative, comparable to that for sulphur. On the other hand, at lower oxygen levels, the results indicate that the interaction parameter values are positive. The results are discussed in the light of some of the theoretical models for solute interactions in liquid metals.

Jan 1, 1993

By Ralph H. Nafziger

The feasibility of smelting a Ni-Co-Cr-bearing laterite ore from southern Oregon was evaluated by the Bureau of Mines. The objective was to prepare a master alloy for subsequent stainless steel production. A mixture of the ore with suitable reductants and fluxes was smelted in a 50-lb-capacity single-phase ac electric furnace under sub- merged arc conditions. The smelting tests produced a metal in which most of the nickel was concentrated. High-chromium recoveries required an excess of carbon. The resulting metal alloys contain sufficient nickel for some stainless steels. Ferrochromium additions would be required to attain suitable chromium levels. This research was conducted under the Oregon Metals Initiative in cooperation with Walter B. Freeman.

Jan 1, 1993

By Nickolas J. Themelis

The flash oxidation and smelting of mineral sulfides is a very prominent metallurgical achievement of the second part of this century. Its initial industrial implementation owes much to the work of Petri Bryk, in Finland, and Paul Queneau, in Canada. However, attempts to develop flash reduction pro- cesses, such as the reduction of iron oxide concentrates with hydrogen, have not yet been successful. The author, on the basis of experimental studies on both kinds of flash reaction systems, examines the respective rate controlling phenomena and the relative rates of flash oxidation and flash reduction.

Jan 1, 1993