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By Rashmi Kumar, Amit Chatterjee, Sanjay Chandra

The practice of adding alloying materials to a molten bath is an integral feature of many pyrometallurgical operations. However, very little is known about the dissolution rate and solution mechanisms of solid additives in liquid melts. In foundries where large tonnages of liquid metals are handled, there is considerable interest in achieving optimum metal quality at minimum cost. This objective is influenced by several factors and the solution is often plant specific. Though the amount, sequence and mode of ferroalloy addition vary from plant to plant, various fundamental factors determine how quickly these additions dissolve in the bath. At the Ingot Mould Foundry (IMF) in TATA STEEL blast furnace hot metal is used to cast ingot moulds. The composition of hot metal desired for making ingot moulds demands addition of 20 kg each of Ferromanganese and Ferrosilicon in the 12 T transfer ladles into which the blast furnace metal is poured at the IMF. Owing to low temperature of hot metal at the IMF, casting commences immediately and complete dissolution of the ferroalloys is often not possible. To study this aspect in detail and to evolve suitable corrective measures, a mathematical model for the melting of a solid particle in a liquid metal bath was developed at TATA STEEL. The model was validated using the data available in literature. In keeping with published work, two separate dissolution periods were identified - a "shell period" and a "free dissolution period". The maximum thickness of the crust formed around a spherical particle shortly after immersion, can be obtained by using the mathematical model which has been developed. The model can also be used to investigate the effect of various parameters such as superheat of the bath, size of the particle, etc., on the maximum crust thickness and the particle melting time. On the basis of this study, the addition of ferromanganese and ferrosilicon was optimized at the IMF in Tata Steel.

Jan 1, 1996

By K. Soldenhoff

The Bulong deposit, situated near Kalgoorlie in Western Australia and owned by Resolute Limited, is a lateritic deposit containing on average 1.1% nickel and 0.09% cobalt. A process has been developed and tested at the mini-plant scale for direct solvent extraction and separation of Co and Ni from solutions derived by acid pressure leaching of Bulong ore. In this paper, two solvent extraction processes are described. The first process uses Cyanex 272 to extract cobalt and reject nickel to the raffinate. The second process uses Versatic 10 to extract and purify nickel. The loaded strip nickel solution is suitable for electrowinning. Results of both batch laboratory tests and continuous mini-plant trials are presented. The selectivity of the solvents with respect to the major impurities such as Mn, Mg, Ca, and Zn is also discussed.

Jan 1, 1998

By T. K. Mukcherjee

The importance of the processing of secondary resources such as solid industrial wastes and liquid effluents as well as byroducts for the recovery of the associated metal values hardly needs any elaboration. Such processing contributes in no small measure.towards the augmentation of the availability and the supply position of resources. As an added benefit, it leads to a reduction in environmental pollution caused by the undesirable waste materials. As some typical examples of secondary resources in the Indian scenario, mention' can be made of spent catalysts, metal/alloy scrap, ash, consumed batteries, flue dust, slag, sludge and slime, pickling solutions, spent acids; plating rinse solutions, spent etchants, waste water from synthetic fibre manufacture and from tanneries etc. These wastes constitute a source of a variety of non ferrous metals. In the processing of secondary resources like these, the techniques of hydrometallurgy such as solvent extraction play a pivotal role. This paper outlines the efforts made to use solvent extraction to recover(1) base metals. such as copper, zinc, nickel and cobalt from a number of secondary resources like cake, and sludge(2) refractory metals like molybdenum and vanadium from sulphidic byproducts and spent catalyst and (3:) nuclear metal like uranium from phosphoric acid. In the case of base metals, process flowsheet involving the use of acidic extractants such as DEHPA and PC88A have been optimised. The problem of iron removal from the leach liquor, "which influences the metal recovery process significantly, has drawn a special emphasis. hi the case of refractory metals, basic extractants .like Alamine 336 has been pressed into service to produce kilogramme. quantities of pure salts of molybdenum and vanadium, Finally, the paper gives a brief account of plant experience in recovering uranium from phosphoric acid, using 'a solvent system comosed of DEHPA and TOPO.

Jan 1, 1996

By L. E. Murr

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

Jan 1, 1976

By G. W. Barton

Process Systems Engineering (PSE) can be defined as the integrated usage of computer-based design and analysis tools. As such, PSE is becoming increasingly important in the chemical and petrochemical industries. This paper shows how a range of PSE techniques have been applied to the zinc electrowinning process. Topics discussed include model development, parameter estimation, steady-state and dynamic model applications, steady-state optimisation and neural network modelling.

Jan 1, 1994

By M. Tomita

One of the most essential factors for a custom smelter to strengthen its competitive power is to Improve its comparative standing in purchase of concentrates from the world market. It is especially critical for Japanese smelters who depend almost 90% of their raw materials on import. In order to accomplish this breakthrough, the development of the new technology which enables us to treat concentrates containing higher Impurities is inevitable. Nippon Mining Company Ltd. made an intensive research on processing complex ore for three years from 1979, and successfully developed an original hydrometallurgical process to treat converter dust for eliminating impurities from the copper smelting circuit. The commercial plant was constructed at the Saganoseki Smelter & Refinery in 1982, and its nine years operation has been satisfactorily proven the advantages of the technology. The concept of this process and its operational performance are discussed.

Jan 1, 1992

By Pandey H. D.

The paper describes a fluidised bed ion exchange method for simultaneous removal of phenols and cyanide from the effluent. Use of an eluant enables regeneration of the resin in the continuous operation mode. The breakthrough experiments conducted both on the laboratory scale and on a pilot plant scale have shown that while the level of phenol can be brought down from 462 ppm to about 6 ppm, the free cyanide is almost totally removed. An examination of data indicates that the method can serve the twin objectives of pollution control and phenolic compounds recovery.

Jan 1, 1992

By Yasuyuki Murayama

MF is the semi-blast furnace which has been developed at Mitsui Miike Smelter in the 1960's to treat vertical retort residue. The MF has also been tested for treatment of various recycling materials and wastes. Now various secondaries and wastes (steel dust, zinc leaching residue, Cu-Ag sludge, spent catalyst and spent rubber, etc.) are mainly treated. Powder materials are briquetted with reductant before being fed to the furnace. Products are crude zinc oxide, matte, non-hazardous slag and steam. Zinc and lead are recovered in oxide dust, and copper and silver are recovered in the matte. The MF furnace can be widely applied to many kinds of materials which contain such non-ferrous metal-valuables. In addition, the improvement in operation and technology has effectively made the unit capacity much larger. The MF furnace now has many advantages for these treatment processes.

Jan 1, 1992

By David N. Hanlon

The effect of high-temperature plastic deformation of the austenitic phase (y) on the subsequent phase transformation to ferrite (a) has been experimentally investigated, and modelled using a physically-based model. The effect is of importance for steel sheet, in view of me significance of the phase transformation with respect to the eventual properties of the material. In this paper the kinetics of the y ? a phase transformation has been studied after different degrees of prior deformation. The degree of deformation is varied by applying different deformation temperatures and strain rates, and by allowing a varying extent of recovery and recrystallisation. Consequently, both dynamic and static recovery and recrystallisation have been involved. The dilatometric observations on the phase transformation have been modelled using an interface-mobility model, in which the effect of the dislocation structure is introduced as an additional driving-force term. The effect of the stored energy on the nucleation process, which appears to be affected more strongly than the growth of ferrite, is examined in terms of the classical nucleation theory.

Jan 1, 2001

By Patrick R. Taylor

This investigation studied the inflight calcination kinetics of nuclear waste simulant using a thermal plasma reactor. A series of experiments were performed to determine the conversion of insoluble aluminum compounds to the soluble compounds and the decomposition of complex organic and nitrite compounds present in the simulant waste. Thermodynamic calculations based on free energy minimization were performed to establish a theoretical basis for this investigation. A kinetic model to describe the conversion of gibsite to sodium aluminate has been proposed. The products of the calcination were characterized using XRD, Gas Chromatography, and chemical analysis by ICP. The results of this investigation indicated 85% gibsite conversion to sodium aluminate, 90% of nitrate decomposition, 52% TOC decomposition and 90% conversion of chromium to soluble compounds. A process is identified for inflight calcination of wastes. Key words: Plasma, waste, simulant, calcination

Jan 1, 1996

By D. G. C. Robertson

The thermodynamics and kinetics of the reactions involved in fuming zinc from oxide slags using coal or coke were first studied in 1955 and have been the subject of many investigations since that time. The key reaction is ZnO(in slag) + CO Zn(g) + COl. This paper will review the some of the recent work, and will add new insights obtained in experiments carried out by the authors. In the first series of experiments it was shown that the reaction 2Fe2+ + ZnO = 2Fe3+ + Zn(g) or 2FeO + ZnO = Fe2O3 + Zn(g) does not occur at an appreciable rate, as is expected from thermodynamic considerations. In the second series of experiments it was shown that zinc does not fume from the slag at a significant rate unless a reductant has been added. This again is in accord with thermodynamic considerations, but is in contradiction to some of the experimental results reported in the literature. A third series of experiments was carried out with excess coke being present, so that the rate of supply of reductant was not in any way controlling the rate. The kinetics of zinc oxide reaction were then found to be independent of the zinc oxide concentration, but increased with increasing basicity, and temperature. The presence of high concentrations of FeO in the slag also improves the kinetics. At low zinc oxide concentrations iron oxide reduction occurred in parallel with zinc oxide reduction. We propose that (under the conditions of this work) the kinetics were controlled by a chemical step, namely the rate of desorption of an adsorbed CO2 species. This is the same mechanism as reported by Belton and co-workers for the kinetics of the reduction of FeO. This explains why the reduction of metal oxides in slags by hydrogen is often faster than by CO.

Jan 1, 2003

By V. Baltazar

The behaviour of arsenic and antimony during copper electrorefining was studied in order to identify the conditions under which good quality copper cathodes could be produced from anodes with high levels of these impurities. Examination of the effect of current density over the range 21 to 37 mA/cm2 indicated that the relative amounts of As and Sb entering the electrolyte affected the onset of passivation. When the ratio of As/Sb entering the electrolyte was greater than 2, the anodes showed no sign of passivation even at the highest current density; when the ratio was less than 2, the anodes passivated at 37 mA/cm2. Cathode analyses showed that anodes with an As/Sb dissolution ratio less than 2.0 tend to produce cathodes of inferior quality even at normal current densities (25.7 mA/cm2). The criterion of a minimum As/Sb dissolution ratio of 2.0, and mathematical correlations for the distribution of As and Sb between the electrolyte and slime developed in a previous study, allow the calculation of the maximum allowable Sb level in en anode for a given As concentration. Analyses of plant data at the CCR Division of Noranda Inc. for the last four years of operation have demonstrated that the use of this as a quality control tool has allowed the quality of copper cathodes to be maintained despite a significant increase in the average Sb levels in anode receipts.

Jan 1, 1987

By Toru H. Okabe

As part of a systematic study on the thermodynamic properties of complex nitrides, phase equilibria of the system Li-M-N (M Mg, AI, Ga) at 900 K were investigated. An attempt to determine the thermodynamic properties of complex nitrides was made by using the galvanic cell method, which utilizes LiMgN as an electrolyte under nitrogen atmosphere. The electromotive force (Emf) of ilie cell at temperatures between 800 and 1100 K was measured. Whilc the Emf of the cell at 900 K was measured to be 0.137 V, data discrepancies of ±0.03V were found. It was difficult to determine temperature dependence of ilie Emf. The Gibbs energy change for the reaction, 113 LbN (s) + 1/3 Mg3N2 (s) = LiMgN (s), at 900 K was determined to be tJ.Gor (LiMgN) -13.2 (±2.9) kJ/mol. Using thermodynamic information on ilie binary nitride from literature, the standard Gibbs energy of LiMgN was derived to be AGO f (LiMgN)= - 121 kJ at 900 K. The thermodynamic stability range of nitride was discussed by constructing isothermal chemical potential diagrams that provide a better understanding of ilie stability region of the LiMgN phase. The diagram was found to be in good agreement with the isoiliermal phase diagram determined by ilie alloy equilibration meiliod. Although the obtained data includes large uncertainties, the results provide a better understanding of the iliermodynamic stability of nitrides. The potential application of this complex nitride to nitrogen chemical sensors or a medium for controlling nitrogen potential is also shown.

Jan 1, 2003

By R. J. Mitchell

Results from investigations into impurity distributions over cathodes are presented with implications for various sampling methods, Selection of an optimum treatment procedure for the test sample is outlined. The impact of both these studies on the development of an in-house method for sampling Isa Process cathode is discussed. The economic compromise actually undertaken, satifying wants and needs to sustain confidence in high grade cathode purity is detailed.

Jan 1, 1987

By Kazuki Morita

Dissolution mechanism and solubility of chlorine in the oxide melts, such as CaO-SiO2-Al2O3 (-Na2O), Na2O-SiO2-Al2O3 and CaO-SiO2-FeO systems, have been equilibrium technique was employed with controlled Po2 and PCl2, (Po2 = 10-6 -10 19 atm, PCl2 10-6 -10-13 atm at 1673-1748 K). The solubility of chlorine in the 40mass%CaO-40mass%SiO2- 20mass%Al2O3, slag was found to vary in proportion to Pb2/ w and pc/z/p' which proved that chlorine dissolved in the melts as C1 anion. Hence, the chloride capacity (CCI-), indicating the ability of molten oxide to absorb chlorine, has been defined as; The Ccl value was observed to increase with increasing slag basicity and temperature, and showed a reasonable relationship with that Of CS2-. Based on the result obtained in the present study, chlorine distribution during incineration with slags was predicted quantitatively.

Jan 1, 2003

By Garry W. Warren

The brass foundry industry produces a significant amount of waste sand containing Cu, Zn and Pb which is often classified as a hazardous waste due to Pb content. The potential application of a hydrometallurgical process to treat the sand by extracting metal values and thus detoxifying the material has been investigated. The process involves leaching of metal values followed by cementation. The emphasis of this investigation was on the leaching step, although some preliminary cementation experiments have been performed. In order for any alternative treatment scheme to be successful, the smaller size fractions of the sand must be addressed. Experiments have been performed on five individual size fractions using various lixiviants HCI, acetic acid and HCI/NaCI. Cu extraction was found to be slower than either Zn or Pb. Results obtained in this investigation indicate that copper is present in two forms, an oxide form which dissolves rapidly and is insensitive to the level of oxygen, and a less soluble form, probably metallic which dissolves more slowly and requires an oxidizing agent. The presence or absence of oxygen had no influence on the rate of Zn dissolution indicating that zinc is present mostly in oxide form. Toxicity Characteristic Leaching Procedure (TCLP) tests showed that residues could be produced which meet the toxicity limit for lead. Preliminary cementation experiments have also demonstrated the feasibility of Cu and Pb recovery.

Jan 1, 1991

By Y. Maeda

Non-ferrous smelting furnaces generally lnstal1 a gas cooling system for treatment of waste gas containing S02. From the point of view of corrosion resistance and recovery of waste heat, the high pressure boiler system Is the best way to cool gas, however this system requires high Initial investment and relatively higher operating costs. Because the feasibility of this boiler system greatly depends on the smelting process and scale, other lower temperature systems, e.g. water-cooled Jacket system, are more suitable If the smelting process does not produce enough steam nor generate enough electricity to compensate operating cost. In addition, the water-cooled Jacket system Is simple in structure and easy to operate. For those reasons, it is applied widely. A new smelting furnace. was planned tin our factory and It was necessary to install waste gas cooling equipment. In our case, a water-cooled Jacket system was mo11e feasible because of the low gas volume and high dust content. H was also expected to operate without maintenance for ten years. On the other hand, some leakage problems with the water-cool1ed Jacket had been experienced In the past. That is because S02 in the waste gas changed into sulfuric acid which corroded the Jacket material, As the first step, several data from actual usage were reviewed to throw light on the corrosion process, and an appropriate procedure to determine the operating temperature of cooling water was obtained. For the basis of this study, a water-cooled Jacket system was newly designed and tested for three months in a pilot plant. After this system's performance was confirmed, It was installed In a new furnace as a commercial pl.ant. After one year of operation, the initial thickness of carbon steel Jacket remains almost the same.

Jan 1, 1992

By Zdzistaw MiGzkowski

At KGHM Polska Miedi S.A. a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass ex-change inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed. The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ? The second zone moves slower into the grain and the rate of the movement is deter-mined by the presence of oxygen. In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined. The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By Takahiro Miki

Soldering material widely used is Sn-Pb alloy, which have low melting point and excellent electrical, strength properties and wettability. However, Pb is one of the toxic elements, which is undesirable due to environmental and safety reasons, thus Pb-free alternative alloy is preferred for new soldering material. Sn-Ag and Sn-Zn based alloys have been viewed as very promising candidates, among many potential substitutes. Addition of third element to these alloys will decrease melting point of the alloys. Hence, Sn-Ag-In and Sn-Zn-Mg alloys are expected to be suitable for replacing Sn-Pb solder alloy. In order to design new Pb-free soldering materials, it is crucial to understand precise thermodynamic properties and phase diagrams of alloy systems. In the present work, ion current ratios of Ag to In and Mg to Zn were measured for Sn-Ag-In and Sn-Zn-Mg alloys by mass spectrometry, respectively. Also, the authors reviewed the thermodynamic properties of terminal binary alloys determined by other researchers and evaluated a thermodynamic functions to express the excess Gibbs free energy of each binary alloy. Thermodynamic functions to express the excess Gibbs free energy of liquid Sn-Ag-In and Sn-Zn-Mg ternary alloys were determined, utilizing the assessed Gibbs free energy of terminal binary alloys with the measured ion current ratios using mass spectrometer.

Jan 1, 2003

By D. W. Collins

The uptake of gold from halide solutions by activated carbon has been investigated using various techniques. Halide systems typically exhibit combined adsorption-reduction type behavior. In an attempt to gain more information about the nature of these processes, samples of synthetic highly-oriented pyrolytic graphite (HOPG) were contacted with aqueous solutions of gold-iodide. HOPG represents a model structure for activated carbon comprising of basal- plane sites, edge sites, and various defect sites. Two basic instrumental methods were used to examine the uptake of gold by HOPG. The first was standard X-ray photoelectron spectroscopy (XPS). The other involved several scanning probe techniques. XPS clearly indicated a preferred uptake of gold at edge sites. However, iodine appeared to be distributed on both basal-plane and edge sites. At low iodine additions, tapping mode AFM showed that clusters were concentrated along steps and surface defects. At high iodine concentrations, the HOPG surface was uniformly covered by iodine.

Jan 1, 1998