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By Jochen Petersen

Design and operation of heap leach processes are still largely based on,operator experience and rule of thumb. Although considered a low-cost, low-tech route for mineral extraction, the underlying physical, chemical and biological processes are actually rather complex. Numerous heap leach models have been devised over time, but the majority of these tend to simplify the true process and are of limited use in practise. The modelling approach presented here combines the more conventional reaction-diffusion model with models accounting for equilibrium reactions in solution, bacterial growth kinetics, complex reactions schemes, gas flow, heat conservation, etc. One particular model application is discussed in the context of developing a novel high temperature heap leach processes using thermophile micro-organisms. The complexity of processes such as this can only be appreciated with the aid of a systematic model. For the designing engineer an accessible, personal computer based model should be an indispensable tool for the design and optimisation of efficient heap leach operations.

Jan 1, 2002

By T. K. Mukherjee, C. K. Gupta

"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 playa 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. In the case of refractory metals, basic extractants like Alarnine 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 T. K. Mukherjee

The importance of the processing of secondary resources such as solid industrial wastes and liquid effuents 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 Malsuzaki. Kenji

A mathematical simulation model of the Imperial Smelting Furnace operation has been developed for purpose of improving the furnace operation. The model consists of top, shaft and bottom regions. Analysis in the shaft region is based on differential heat and materials balances taking account of reaction kinetics and heat transfer rates, and those in the top and the bottom regions are based on heat and materials balances under a steady-state condition. Longitudinal distributions of process variables such as temperatures of gas, sinter and coke, gas composition and fractional conversion under a practical operating condition were calculated. With this model, the furnace performance under various operating conditions also can be shown reasonably predicted.

Jan 1, 2003

By Kenji Matsuzaki

A mathematical simulation model of the Imperial Smelting Furnace operation has been developed for purpose of improving the furnace operation. The model consists of top, shaft and bottom regions, Analysis in the shaft region is based on differential heat and materials balances taking account of reaction kinetics and heat transfer rates, and those in the top and the bottom regions are based on heat and materials balances under a steady-state condition, Longitudinal distributions of process variables such as temperatures of gas, sinter and coke, gas composition and fractional conversion under a practical operating condition were calculated, With this model, the furnace performance under various operating conditions also can be shown reasonably predicted,

Jan 1, 2003

By Baicheng Liu, Houfa Shen, Wensheng Li

"In order to understand the formation of macrosegregation in steel ingots, a mixture model has been developed which accounts for coupled mass, momentum, species, and energy transport to describe the sedimentation of free equiaxed grains during solidification. In this model, the mushy zone is divided into the slurry and porous regimes according to a solid packing fraction. Settling velocity of equiaxed grains in the slurry regime is given by an explicit expression. The solidification of a binary steel ingot (Fe-0.36wt.%C) with a two-dimensional geometry is numerically simulated. It is demonstrated that the predicted macrosegregation patterns agree to some extent with classical experimental results. Further refinement of this model is still necessary for realistically simulating steel ingot solidification.IntroductionModeling macrosegregation in steel ingots is still a challenging study, mainly due to the length scale of the products and the complexity of global multiphase transport phenomena coupled with microscopic solidification kinetics [l]. The thermal-solutal convection and the motion of equiaxed grains are the two main mechanisms responsible for macrosegregation. But there are few models that deal with the motion of equiaxed grains, which is confirmed as the main phenomenon that explains the negative macrosegregation along the centerline of large steel ingots [2]. A model which takes into account melt convection and grain sedimentation was first proposed by Beckermann and co-workers ([3], and references therein). More recently, similar multiphase solidification models with advanced nature have been presented by Wu and Ludwig [1,4] and Combeau and co-workers [5,6]. It is known that the application of these sophisticated models to steel ingot casting is at its beginning.In this paper, a solidification model based on continuum mixture approach, using much less sophisticated relations to obtain the settling velocity of free equiaxed grains, has been proposed in order to predict the macrosegregation in steel ingots. The model is applied to simulate the solidification of a binary steel ingot with a two-dimensional geometry, and preliminary modeling results are presented."

Jan 1, 2011

By Vaughan R. Voller

"Over the last ten years an increasing number of heat and mass transfer models of solidification processes have been presented in the literature. A key component in these models is the coupling between thermal and solute fields. This is achieved by developing relationships based on the behavior at the microscopic scale in the casting (typically a secondary dendrite arm space). An important class of models in this respect are models that describe the local scale redistribution of solute alloy components-collectively referred to as microsegregation models. This paper explores this class of models.IntroductionModeling takes a key role in processing materials for properties. This is particularly time in solidification processes where current computer techniques allow for a detailed treatment of the critical macroscopic phenomena. Typically these macro scale models consist ·of three main coupled components.1. A model of flow in the melt and solid + liquid mushy region.2. A model of heat transfer.3. A model of solute transport.The focus of this paper is the solute transport component, in particular the manner in which process scale transport is coupled to transport ·at the local scale of the solid-liquid interface. This step requires a modeling of the redistribution of solutes at the scale of the secondary arm spaces in the dendritic mushy region-a process referred to as microsegregation. Basic microsegregation models use the limit assumptions of no mass diffusion in the solid (Gulliver-Scheil [l]) or complete diffusion in the solid (equilibrium lever rule) in a fixed and space. Recently, however, more sophisticated microsegregation models that account for finite mass diffusion and coarsening of the arm space have been developed [2-19]. In this paper governing equations for a general microsegregation model for a multi-component alloy in a coarsening and spacing _are introduced. From these general equations various models for a binary system are developed and tested"

Jan 1, 2000

By Renato G. Bautista

The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions:. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.

Jan 1, 1996

By Jinxing Ji

Several fundamental aspects related to the nickel electrowinning from chloride electrolytes have been addressed in this paper. The thermodynamic study includes the activity coefficient of the hydrogen ion and the speciation diagram of NiCI2 solutions. The activity coefficient of the hydrogen ion (YH+) was calculated and estimated experimentally using a combination glass pH electrode. It was found that YH+ was greater than one in concentrated NiCl2 solutions and increased significantly with increasing NiCl2 concentration. The speciation diagram for NiCl2 solutions was plotted with YH+ and the effect of the ionic strength on the equilibrium constants being taken into account. It was discovered that the predominant nickel species in the acidic region were Ni2+ and NiCI+ in 0.937 M NiCl2 solution at 25°C. Electrodeposition tests demonstrated that higher Nit' concentration in the electrolyte improved the current efficiency of nickel electrodeposition (CENi). The additions of H3BO3, and NH4Cl increased very little the current efficiency of nickel electrodeposition at pH 1.5 and temperature 60°C. However, the addition of sulfate decreased the current efficiency of nickel electrodeposition. Nickel electrodeposition was also found to be a steady-state process since the amount of acid added to the electrolyte at a constant pH increased linearly with time during galvanostatic electrodeposition. The cathode surface pH during nickel electrodeposition was measured using a flat-bottom combination glass pH electrode and a 500-mesh gold gauze as cathode. The cathode surface pH was found always to be higher than the pH in the bulk electrolyte, and if the current density was sufficiently large, it would eventually reach a level causing precipitation of insoluble Ni(OH)2(s) on the cathode surface. Rotating disc electrode studies revealed that the rate of nickel electrodeposition was first order with respect to the activity of nickel ion and zero order with respect to the activities of chloride and hydrogen ions. The rate of hydrogen evolution was found to be first order with respect to the activity of hydrogen ion and to be zero order with respect to the activities of nickel and chloride ions. These findings indicate that nickel deposition and hydrogen evolution proceed independently.

Jan 1, 1995

By Evgueni Jak

Recent advances in analytical, experimental techniques, and computer-based theoretical modelling of fundamental properties and elemental processes, provide new opportunities to develop the next level of whole-of-reactor pyrometallurgical furnace models. These models have the potential to significantly improve the prediction of, and adding value to, industrial operations. In non-ferrous smelting, the starting point of these models is the development of multicomponent thermodynamic databases for gas-slag-matte-speiss-metal-solids phases supported by systematic experimental research. The whole-of-reactor-models additionally should take into account kinetic processes taking place at micro- and macro- scales, and other key factors. Examples of applications of the latest research tools and modelling approaches to analysis of industrial flash and top submerged lance (TSL) sulphide smelting processes are presented. Different levels of industrial modelling are discussed from elemental local reactions, through general and more detailed whole-of-reactor-models, to plant sections and further to whole plant operation models. Some principles for development of pyrometallurgical reactor models are discussed.

By Renato G. Bautista

"The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.IntroductionThe understanding and the elucidation of the mechanism of the rate phenomena for a specific chemical reaction system is of prime importance in the development of a successful chemical process. The development of successful emerging technologies for metals separation will depend on the accurate interpretation of the intrinsic chemical reaction kinetics and the rate of mass transfer of the desired metal species during its separation from the undesirable chemical species. This is the case whether the process application is for separation, concentration, and /or purification.The chemical processes that will be examined in this presentation will include leaching, solvent extraction, membrane separation, precipitation, and electrodeposition."

Jan 1, 1996

By Douglas J. Harvey, Chi-Mou Ni

"This paper presents an analysis technique for the solidification of metal castings. This method, based on a modified finite difference scheme with an irregular mesh, is capable of dealing with the complex geometries of castings. The nonlinearities in material properties of specific heat and thermal conductivity, arising from the phase change during solidification, are accounted for in the step-by-step calculations. Two solidification problems are solved with this analysis technique and the calculated results compare satisfactorily with experimental data. IntroductionCasting process design engineers are often faced with the difficult problem of designing castings to be produced porosity-free. Since the solidification of metal is affected by many interacting variables such as the thermal conductivity, density, and specific heat of both the molten metal and the mold, it is easily seen why this is a difficult task.Typically, casting tooling design is an intuitive process which builds on past successful methods. After processing equipment is constructed, trial castings are made and examined for dimensions and integrity. Changes in the tooling are generally required to improve casting soundness or to reduce cycle time. In the permanent mold process, tooling is complex and difficult to alter after initial construction. The water-cooled steel molds are part of the complete automated system. Associated holding furnaces, pouring ladles, casting conveyers, and utility connections all make other than minor adjustments a costly and time consuming task. An analytical method for using the principles of heat transfer for predicting solidification patterns would be of great value in the permanent mold process by minimizing costly changes."

Jan 1, 1986

By R. L. Nyirenda

The use of ammoniacal ammonium carbonate (AAC) leaching for the treatment of carbon steelmaking EAF dust has been investigated on a laboratory scale. The experiments have been conducted on dust samples obtained from three European steelmaking companies. As received, the dusts were found to be toxic when tested according to current EPA toxicity testing procedures. Toxicity was on account of the leachability of one or more of the following elements: Ag, Hg, Pb, and Cd. Leaching experiments with concentrated AAC solution at 40 " C showed that zinc oxide present in the three dust samples, 60-80% of the total contained zinc, was rapidly solubilized. Data on the dissolution characteristics of Cd, Fe, Pb, Mg, and Mn are also presented. Toxicity tests conducted on residues of the leaching experiments found these to have leachates below past and current EPA toxicity threshold limits.

Jan 1, 1993

By B. Zilbergleyt

Current understanding of chemical equilibrium is based exclusively on the probabilistic considerations that are correct for isolated systems with only one chemical reaction to take place. For the systems with multiple chemical interactions, current paradigm of chemical thermodynamics promotes the idea of openness, artificially flavored with coefficients of thermodynamic activity. Recently introduced thermodynamics of chemical systems and the Method of Chemical Dynamics (MCD) offer explicit accounting for the multiple chemical interactions within the system. In the new theory, thermodynamic equilibrium of the j-subsystem obeys the logistic equation derived exclusively from the currently recognized concepts of thermodynamics. Having the only one new parameter -the subsystem's reduced chaotic temperature 'tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system's possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the 'tj value. The MCD brings new opportunities to thermodynamic simulation of complex metallurgical and chemical systems, allowing for the analysis of their domains of states and the area limits, and for more accurate calculation of the equilibrium compositions. Its usage is exemplified in this paper by several applications. Keywords: chemical thermodynamics, open systems. complex systems, chemical dynamics.

Jan 1, 2003

By Hong Ouyang

A unified computational model has been developed for the Bridgman growth processes of B-NiAI and CdTe crystals. To handle the geometrical and physical complexities, a two-level approach has been developed. At the gtobatlevel, conjugate heat transfer, phase change dynamics, and variable material properties along with the realistic geometries and thermal boundary conditions are accounted for inside the entire crystal growth system. Refined calculations are then made within the ampoule, with the boundary conditions supplied by the global simulations. This model can optimize the use of computational source, help understand solidification behaviors, and improve designs of crystal growth system.

Jan 1, 1996

By Alexander I. Raitchenko

"Although one takes into account only thermal expansion usually at analysis of convection onset, the essential factors include magnetic and electric fields. If Lorentz-force originating from intercrossed electric and magnetic fields' action is directed downwards its effect strengthens gravitational action, and value of critical Rayleigh number (limit value for convection onset) must decrease; increasing of critical Rayleigh number should be observed in case of Lorentz-force directed upwards. Extent of such an influence is determined by relation of Lorentz-force to hydrostatic head in gravitational field. Competition between electromagnetic force due to nonuniformity of electroconductivity (on account of its temperature dependence) and electromagnetic buoyancy force may have ambiguous effect: both increase or decrease of critical Rayleigh numbers. Proposed conception is applicable to analysis of situations in liquid conductors and conductive gases.IntroductionStatic or dynamic situations in fluid media are determined besides properties of these media by a variety of external influences. However one correlate~ the onset of the convection and its development with influences of the minimum quantity of external causes frequently. Most known and usual factors are the gravitational and temperature fields. The number of processes includes heat generation in media volume, and theoretical analysis in these cases takes into account this interior heating together with boundary temperature conditions. But explanation of many natural and technical events is not complete and cogent within limits of thermo-gravitational terms. The whole complex of acting factors which influence convective processes in techniques and nature is greater in many cases. In particular the action of · electromagnetic nature often has not less importance than gravitation one. Stability or instability of a current layer in the plasma must be determined by non-uniformity of electroconductivity owing to non-uniformity of temperature [1]. The presence of Joule dissipation in the plasma through which the electric current flows stipulates initiation of origin of overheated instability [2]. It is known that electroconductivity of arc in the boundary zone changes sharply with radial distance [3], and this must influence its stability essentially. If the intercrossed electric current and magnetic field begin to act on an electroconductive fluid besides the non-uniform temperature field and the gravity, the conditions for the onset of the convection change radi- . cally: both the temperature field and their solutions have to be changed also. The analysis of equilibrium single-time correlation functions of fluctuations must be employed for situations with enlarged number of factors as this was in case for the Rayleigh-Benard problem where the object is a horizontal layer of liquid. This can be carried out by taking into account the detached forces' correlations [ 4, 5]"

Jan 1, 1999

By E. T. White, Dean Ilievski

"The population balance is one of the basic relations for analysing particulate mineral processing operations. It is an exact relation. The principles of the population balance are reviewed and applications in the minerals industry discussed.IntroductionMathematical modelling has proved to be a very successful approach for improving the design and performance of mineral processes, particularly since the availability of computers to handle the complexity usually necessary to give a useful model.Mineral processes almost invariably involve particles, as either solid fragments, liquid drops or bubbles. Process performance usually is highly dependent on the behaviour of these particles. In modelling particle behaviour, the basic relation to be used is the population balance. This paper discusses the role of the population balance and the range of its applications in minerals processing.The Population BalanceThe population balance was developed for demographic studies, ego predicting the change in the population (numbers) of, say, school children between one census and the next. The first sustained application to the processing industries appears in the 1960s for crystallization. However it was recognised almost immediately that it had application to all particulate processing."

Jan 1, 1996

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 C. J. Parradies

During injection into a die, semi-solid metal alloys exhibit a shear-rate, history-dependent flow response. Simulating the injection of a thixotropic material requires that empirically determined boundary conditions and viscosity are specified as a function of both temperature and shear rate history. Experiments were performed using an industrial die casting machine that was instrumented with sensors to measure the pressure and temperature during the injection of a semi-solid aluminum alloy through a tube. This benchmark experiment was used to develop a simulation of the die casting process that could then be applied to more complex die geometries. The results of the experiments were analyzed using the exact, steady state solution for a power law fluid and simulations accounting for slipping at the boundary between the semi-solid metal and the die. Results indicated that the no-slip condition cannot be used to simulate the velocity boundary condition, because the measured pressure is much lower than that predicted by the models. An estimated apparent slip coefficient was introduced to account for the reduced pressure. During some of the experiments, a sudden drop in the measured pressured, prior to decreasing the ram velocity, coincided with observations of segregation in the form of concentric rings visible on the polished surface of cross-sections cut from material remaining in the tube.

Jan 1, 1997

By B. G. Thomas

"Mathematical process models can be applied in several different ways to serve industry by inducing beneficial changes to process operation. This paper attempts to summarize the different uses, types, and attributes of these models, and to offer some ideas to consider when developing, using, and reporting on them. Process models range from empirical to mechanistic in nature and vary in complexity from simple analytical solutions to coupled, 3-D transient numerical simulations. They are classified here according to the way in which they are implemented in practice, viz. fully-online models, semi-online models, off-line models, and literature models. The purpose of the model should dictate how choices are made during its development. Ways to validate and compare the model with experiments are suggested. Examples are taken in the context of the author's experience in modeling the continuous casting of steel.IntroductionThe objective of this paper is to provide a partial introduction for this symposium by discussing some basic aspects of the application of mathematical process models in industry. Essentially, the aim is to explore how process models are used to benefit industry, and to offer some general comments and suggestions, based on the experience of the author, on how models can best meet this goal.This work is concerned with process models, which consist of systems of mathematical equations and constants that are solved on a computer to make quantitative predictions about some aspect(s) of the process. The specific variables required as input data and generated as output data are important features of the model. The equations often derive from a numerical solution to one or more differential equations and their boundary conditions. The model also includes the constants, which represent material properties, empirical relationships, and other knowledge about the process, and usually require considerable effort to obtain. Thus, general purpose commercial software packages, (ie. finite-element or finite-difference based codes), are not models in this context. They are useful tools, however, serving as frameworks for the development of process models."

Jan 1, 1994