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By S. M. I Kytö, J .. K. Mäkinen, K. Saarhelo

"At the Outokumpu Oy Harjavalta Copper Smelter the control philosophy of the flash smelting process has been changed from the slow feed-back control to feed-forward control. This is important as the fluctuations in the flash smelting furnace matte grade and slag temperature are desired to be minimized.The system is based on a specially designed automatic sampling device and the Outokumpu Courier 20 on-stream X-ray fluorescence analyzer. A microcomputer-based Analyzer Operator Station (AOP) controls the system and calculates the process parameters for the furnace from the analyzed chemical composition and other existing data.A considerable reduction in the deviation of the matte grade and slag temperature has been gained. This has resulted in conservation of energy and refractories, lower copper losses and higher through-put in the flash smelting furnace and converters.1.0 IntroductionThe flash smelting technology for copper concentrates was developed at the Outokumpu Oy Harjavalta Smelter soon after the World War II. The incentive for this development was shortness and high price of any form of energy. The fact that smelting can be carried out autogenously, without external energy by utilizing the latent heat of sulfide combustion was known decades before, but Outokumpu Oy was the first company to take the advantage of this knowledge in practical operation. A further advantage of this technology was that the SO2 containing gases suited well for sulfuric acid production, thus minimizing the detrimental effects on the environment (1).The very heart of the flash smelting process is the reaction shaft of the flash smelting furnace (see Appendix I). Heating up of the dried feed mixture, dissociation of several compounds, ignition and oxidation of the feed take place very intensively in the reaction shaft during 2 - 3 seconds, which the fine grained particles reside in the reaction shaft. A very accurate control of the amounts of the feed materials as well as of oxidizing gases, fuel, etc. is of primary importance."

Jan 1, 1989

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' is added. This pretreatment eliminates the refractory nature of concentrates.

Jan 1, 1993

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 Marco V. Ginatta

Current world production, 60'000 ton/y, is exceedingly too small for titanium's extraordinary combination of favorable properties; it should be 1,000,000 ton/y (7% of stainless-steel). Prices that competitively sustain that sales volume are achievable only with electrolytic production, as it is for all other commercial nonferrous metals. But titanium does not have its commercial electrolytic plants yet, because of producers decisions and strategies, scientists works, industrial problems with chloride process, lack of consumers sponsors. Fluoride high temperature process has the advantages of aluminum electrolysis, plus other favorable characteristics specific to titanium and its feed material. One electrolytic titanium potroom replaces several different plants used for sponge production. Production of titanium ingots with zero defect is achieved. The solidified cathode rectangular slabs are suitable for direct rolling.

Jan 1, 2001

By T. Shibaraki

A new larger, more efficient and economical Mitsubishi furnace line at Naoshima was put into operation in May 1991. Naoshima Smelter had produced previously about 230,000 mtpy anode copper with two smelter lines, i.e., a conventional reverberatory furnace line and Mitsubishi furnace line, which had been shutdown at the same time of the start up of the new smelter. At the beginning of the operation, there were several initial problems at the area of off gas trains and feeding system. By overcoming them now the process has been continuing satisfactory operation at the design rate. The paper describes about the design concepts and the actual operation of the new smelter.

Jan 1, 1993

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

By W. H. (Bill) Jay

The destruction of cyanide creates a significant impost on the financial returns of gold mines. These losses increase substantially when ores containing cyanide-soluble copper are treated. Failure to remove or destroy free or WAD cyanide before it is discharged into tailings dams has, on a number of occasions, led to significant fish, bird and animal deaths. Thus, the retention of cyanide within the leach circuit and the recovery or removal of stable metal cyanide complexes needs to become standard practice for all gold mining operations. Furthermore, reducing cyanide purchases will minimise the quantity of cyanide transported to the mine site thereby reducing the opportunity for spillage of this chemical. Many different physical and chemical methods have been investigated for the removal of cyanide from process solutions. All cyanide destruction methods create a financial impost on the economic viability of the gold mine. To reduce these costs, the recycle of cyanide and the economic recovery of the metals solubilised by cyanide is of prime importance. The alternative methods currently in use, or under consideration for the treatment of copper cyanide, entail high reagent costs, produce the recovered metal in a contaminated form and require the safe handling of hydrogen cyanide. These processes will be briefly discussed within this report Environmental and financial benefits are enhanced by recent laboratory and pilot plant studies conducted by Oretek Limited. The Oretek CPC process for the recovery of copper and the recycle of cyanide from copper cyanide-containing solutions does not require pH adjustment to the alkaline cyanide leach conditions. Copper ions are coordinated to a water-soluble and/or an organic soluble polychelating agent under alkaline conditions and the cyanide ions are displaced Membrane separation, or phase separation of the polychelated copper from the cyanide ions enables the cyanide ions to be recycled and the copper to be directly electrowon from the polychelating polymer. The polychelating polymer is then recycled. Ion exchange resins and solvent extraction systems which may be incorporated into the above process will also be discussed in detail.

Jan 1, 1998

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 Sridhar Komarneni

"Microwave-hydrothermal processing is a novel technique which combines the conventional hydrothermal processing with microwave field and we previously showed for the first time, that ceramic powders can be rapidly produced by this technique. This review paper deals with the synthesis of unary oxides such as Fe203, Ti02, Zr02, etc., binary oxides such as BaTiO3, SrTiO 3, PbTiO 3, SrZrO 3, KNbO3, etc., and ternary oxides such as NaTi2 (PO4)3 and pyrochlore phases of Pb(Mg1/3Nb2/3)O3, Pb(Zn1/3Nb2/3)O3 etc. and metal powders such as Cu, Ni, etc. below 195°C. This method can be adopted to the synthesis of a large variety of powders by the appropriate control of pH, Eh, temperature/pressure and concentration of chemical species. The main advantages of this method compared to conventional hydrothermal processing are (a) it increases the kinetics of reaction by one to two orders of magnitude, and (b) it can lead to novel phases especially those with layered structures.IntroductionConventional hydrothermal processing is a well-established synthesis technique which has been extensively used in the preparation of fine ceramic powders [1-5], large single crystals [6-8] and massive cement blocks [9]. Technologically important ceramic powders such as BaTiO 3, Al203 etc. made by the hydrothermal process are now commercially available. Although there are numerous methods for materials synthesis, hydrothermal method is truly a low temperature and environmentally benign process. For example, ZrSi04 (Zircon) which is extensively used in ceramic industry can be prepared hydrothermally at 150·C [10] compared to sol-gel or solid-state method [11,12] which require a temperature of about 1000·C. The hydrothermal method is environmentally benign because hydrothermal reactions are carried out in closed systems at low temperatures and the contents can be recovered and recycled after cooling to the ambient conditions. One of the disadvantages with any low temperature processing method is slow kinetics. For this reason we have combined the hydrothermal method with microwaves to enhance kinetics and we named this method as ""Microwave-hydrothermal"" processing [13- 16]. Although the combination of microwave and hydrothermal techniques has been used in the past few years to dissolve all kinds of inorganic (e.g. alumino silicate rocks) and organic materials rapidly for chemical analysis, we were the first to show its potential value for the synthesis of various ceramic powders [13-16]. In this paper, I show that this novel method is applicable to the synthesis of all unary, binary and multinary oxides by the appropriate control of pH, Eh, temperature, pressure and concentration of chemical species. In addition, this method is also found to be useful for the preparation of metal powders."

Jan 1, 1994

By Paul C. Turner

In 1998, approximately 57,000 tons of titanium metal was consumed in the form of mill products (1). Only about 5% of the 4 million tons of titanium minerals consumed each year is used to produce titanium metal, with the remainder primarily used to produce titanium dioxide pigment. Titanium metal production is primarily based on the direct chlorination of rutile to produce titanium tetrachloride, which is then reduced to metal using the Kroll magnesium reduction process. The use of titanium is tied to its high strength-to-weight ratio and corrosion resistance. Aerospace is the largest application for titanium, and titanium cost has prevented its use in non-aerospace applications including the automotive and heavy vehicle industries.

Jan 1, 2001

By Derek J. Fray

"In order to extend the application of fused salts in\the electrowinning and electrorefining of metals, it is necessary to maximise the current density, minimise the voltage drop and greatly increase the area of electrode surface so as to compete with the space-time yield of pyrometallurgical reactions. The various designs of electrowinning cell are reviewed and it is shown that by the application of a modest centrifugal field it is possible to reduce the anode to cathode interelectrode spacing to 4 mm whilst still maintaining a current efficiency of 85-90%.The thermodynamic potential for electrorefining is far less than for electrowinning yet fused salt electrorefining is only applied in limited cases. The reasons for this are discussed and the important design parameters evaluated. It is concluded that by using packed bed electrodes, separated by a diaphragm, the possibility of electrorefining with very low energy consumption can be achieved. Carbothermically-produced metals are always cheaper than those produced by electrolysis but suffer from the disadvantage of low purity. It is proposed that fused salt electrorefining may offer an energy efficient way of upgrading the metal. IntroductionThe majority of metals can be deposited from fused salts (1,2) but as commercial production is restricted to the more reactive elements, it is worthwhile considering the advantages and disadvantages of fused salt electrolysis as' compared to smelting and aqueous electrolysis. The advantages over aqueous extraction are as follows:1) the much higher conductivities and diffusivities result in much lower IR losses and higher current densities can be achieved at modest voltages;2) the elevated temperatures of operation result in larger exchange currents which give rapid kinetics and lower activation polarisation for the electrode reactions;3) the absence of water as a solvent means that it is not necessary to consider the evolution of hydrogen as a competing cathodic reaction. Furthermore, alkali halide salts, often used as solvents in fused salt electrolytes, have high deposition potentials;4) molten salts generally are mutually soluble and, therefore, concentration polarisation effects are minimised."

Jan 1, 1988

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly. subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fumeless fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts. The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10.1 atm. The concentration ofCu2+ in such slags becomes significant at oxygen potentials of greater than 10'1 atm at 1300 ?C. The activities of CuOo.s and AsOl.S in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of Si02 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2xlO?3 cm2/s at 1350 °C and activation energy of 16 kcal/mol Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300 °c. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material.

Jan 1, 2003

By KNona C. Liddell

The ion interaction model Pitzer proposed twenty years ago is today the most widely used method for calculation of osmotic coefficients and electrolyte and single ion activity coefficients in aqueous solutions. This is due in part to the accuracy of the results that have been obtained for many concentrated electrolytes. An additional factor is that, compared to alternative activity coefficient models, there are many more parameter values available for the Pitzer equations. The important features of this model are reviewed. Published parameter values for Co, Ni, Cu, Zn and Fe are tabulated, and applications of interest in the aqueous processing of these metals are described.

Jan 1, 1993

By N. L. Piret

In copper smelting minimization of solid waste generation is receiving increased attention with more stringent environmental legislation and lower disposal space availability. Copper smelting slags generally being valorizable, solid waste generation is attributed to the presence in the feed of unvalorizable impurities which do not report to the slag and to the unavoidable formation of contaminated dilute acid solutions which need neutralization. As to unvalorizable impurities, solid waste minimization is achieved by rejecting them in the highest possible concentration. Dilute acid is mainly due to the formation of SO3 in the smelter gases and to the discard of decopperized bleed-off electrolyte. Its generation is substantially lowered by preventing SO3 formation, by converting the dilute acid to a valorizable product, e.g., by thermal decomposition for H2S04 recovery or by precipitation as chemical gypsum, and by suitable treatment of the bleed-off electrolyte for impurity removal. Industrial processes are evaluated and alternatives are discussed.

Jan 1, 1994

By Corby G. Anderson

In the majority of industrial operations recovering gold and silver by hydrometallurgical means, cyanide is the predominant lixiviant. However, as an economic alternative, production of massive quantifies of silver chloride was done on an industrial scale in the nitrous-sulfuric acid pressure leaching of a refractory precious metals concentrate. This proven process required no cyanide. Thus, because of the large volumes encountered during day-to-day plant operation, the need for efficient and low cost methods of silver chloride precipitation, reduction and materials handling was mandatory. As such, this paper covers the evolution of plant scale precipitation, filtration, washing, reduction and control of silver chloride processing. As well, an in-depth description of the unique leaching system is included.

Jan 1, 1998

"The theoretical basis of ideal smelting reduction using coal as reductant in a process employing closed loop forced-circulation of hot metal is outlined. In the proposed process, an extensive area of relatively slag-free hot metal is available as a heat sink for absorbing the large amount of heat produced by complete combustion of CO within the furnace. Any slag that is formed within the oxidizing arm of the furnace loop is quickly swept away as a thin floating layer by the bulk movement of hot metal which is induced positively by forced melt circulation and sustained by causing the hot metal and the thin slag layer to overflow into a lower level hearth in which coal is carbonised and dissolved directly into the circulating melt.The proposed process is shown to offer very substantial cost savings over all other direct smelting technology. This is mainly because of its inherently low capital cost and its high energy efficiency. Furthermore, the favourable economics are not reliant on fuel gas credits as all the process gas is combusted within the reactor itself.IntroductionMetallurgical processes in the year 2000 will be compromise solutions to the metallurgical problems that already exist today. It is common knowledge that the mineralogical complexity of certain polymetallic sulphides, for example, precludes high degrees of separation and recovery by conventional mineral beneficiation. steps are therefore being taken towards the development of a truly polymetallic smelting process which will produce simultaneously zinc lead and copper as, metals from complex ores without prior beneficiation(l). In the ferrous extraction industry, the shortcomings of the highly efficient modern blast' furnace are well known and world-wide there is considerable effort being directed towards coal-based ironmaking without the requirement of metallurgical coke as a process intermediate. The current status 0f2Joal-based ironmaking has recently been reviewed by Smith and Corbett. (2)"

Jan 1, 1988

By D. R. Flynn

The recovery of nickel and cobalt from electromachining sludges in the form of relatively high-purity marketable products has been investigated. The investigation has shown that a series of metallurgical unit operations can be performed to recover nickel and cobalt from electromachining sludges in the form of al kal i nickel ic hydroxide and cobalt sulfate/cobal t metal, respectively. The recovery unit operations for nickel include high pH cyanide complexation, followed by oxidation and precipitation of alkali nickel hydroxide. The resultant filtrate can be treated for cobalt recovery by neutralization and acid baking to produce cobalt sulfate. The cobalt sulfate can then be treated for cobalt recovery by electrowinning. Results from laboratory bench scale test work are discussed in terms of appropriate operating conditions.

Jan 1, 1991

By R. J. Kuczynski

The U.S. Bureau of Mines operated a 2,000-9 (4.4-lb) batch process development unit for recovering platinum-group metals (PGM) from automobile catalysts. Virgin monolith, used pellet and used monolith catalyst samples were tested. Leaching twice with 1-pct sodium cyanide (NaCN) solution at 160' C for 1 h in a pressure vessel dissolved over 95 pct of the PGM from virgin catalysts and over 90 pct from used pellet catalysts. Over 85 pct of the PGM was dissolved from used monolith catalysts when a third leaching step was added. PGM concentrates as metallic powder containing over 99.8 pct of the dissolved PGM and analyzing greater than 70 pct PGM were recovered by heating the pregnant leach solutions from virgin catalysts to 250' C and used catalyst to 275" C for 1 h. The solution after heating contained primarily sodium carbonate from cyanide decomposition and less than 0.2 ppm total cyanide.

Jan 1, 1993

By Robert S. Gärtner

The selective aluminum extraction by 3 different calixarenes (p-tert-butyl-calix[4]arene-tetra¬2-acetic-acid-ethyl-ester, p-tert-butyl-calix[4]arene-tetra-2-acetic-acid and p-tert-butyl-calix-[4]arene-di-2-acetic-acid-ethyl-ester) from an industrial pickling bath solution was studied. The pickling bath solution contained hydrofluoric and phosphoric acid as its main components. The aluminum removal was not successful and also no significant extraction of trace metals present was observed.

Jan 1, 1999