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By Helfried Nafe

"For about a century thermodynamically absurd facts have been propagated in conjunction with the iron-carbon phase diagram. These facts concern fundamental relationships of chemical thermodynamics. Attention is turned here to the discussion of only one of the relevant aspects of the subject, i.e. the definition of the thermodynamic activity of the solute and its implications for the iron-carbon solution.IntroductionThe view on the iron-carbon solution is characterized by the assumption that the solute may appear in two different forms, i.e. graphite and cementite. Accordingly, two carbon solubilities are differentiated, on the one hand for graphite and, on the other hand, for cementite. As a consequence, two versions of the phase diagram exist simultaneously, the application of which depends on the prevailing conditions, (i) the so-called stable phase diagram with graphite as solute and (ii) the metastable one that is based on the cementite-in-iron solution. These diagrams are joined together in the double phase diagram that originates from Heyn [l ], with the first ideas mainly going back to Stansfield [2] and Charpy [3].Thermodynamically, the most inadequate implication of the Fe-C double phase diagram is that the carbon activity may take values larger than unity. With the standard state of the activity being that of the pure substance, i.e. the Raoultian one, such a value implies the nonsensical existence ofa state purer than pure. The explanation of this physical state, ifthere is any, vaguely refers to supersaturation and, in the wider sense, to the physico-chemical phenomenon of metastability. Other aspects of chemical thermodynamics are likewise involved. Therefore, the comprehensive investigation into the present subject requires more topics to be considered than only one separate issue. Not only should the criticism of the present view be in the focus but also the discussion of new ideas capable of reconciling the experimental facts, known about the F e-C system, with the fundaments of chemical thermodynamics. All this, however, cannot be provided here because of the limited space available. As a consequence, in what follows only a part of the whole problem is under scrutiny, i.e. the definition of the thermodynamic activity and its role for the interpretation ofrelevant experimental facts."

Jan 1, 2014

By Tapio Ahokainen, Asmo Vartiainen

"Outotec's portfolio contains a wide variety of smelting solutions for non-ferrous metals. Some of these include flash smelting for primary copper and nickel, flash converting for copper, Ausmelt technology for primary and secondary copper, nickel, tin, lead, and zinc residues and waste, Kaldo technology for secondary copper, lead, and precious metals recovery. Outotec also offers slag cleaning technologies and much more.Company provides complete process solutions tailored to each customer's individual needs. Decades of experience have resulted in extensive metallurgical know-how that ensures the most profitable process choice and optimal performance. Outotec's life cycle technology partnership with their customers spans from the early stages of process solution design through the supply and commissioning of the entire process chain. They include integrated process control and holistic service and support concepts. Continuous research and development ensures that the customer is provided with the latest advancements in process and equipment solutions.IntroductionOutotec develops and provides technology solutions for the sustainable use of the Earth's natural resources. Solutions are ranging from various processes and special equipment needed for metallurgical extraction and mineral processing of ores to the production of refined metals and minerals. The processes include not only the grinding and physical separation of ores but also the smelting and leaching of base metals and precious metals. The company provides engineering services for whole projects as well as life cycle services on the equipment and products that they supply."

Jan 1, 2012

By I. Gaballah

Decontamination of synthetic solutions of PbC12 containing 10, 100 and 1000 ppm of lead, using chemically treated barks had been studied. The percentage of !cad cations' removal from solutions depends upon the pH and the initial concentration. About 99 % of the initial lead content can be removed at pH of about 3.5, 5.5 and 6.5 for initial concentrations of 10, 100 and 1000 ppm respectively. The maximum retention capacity of the treated bark is about 83 mg of lead per gram of modified bark. Bark loaded with lead had been analyzed by Infra Red spectroscopy. It seems that lead reacts with hydroxyl groups of the phenolic constituents of the bark. On the other hand, the removal of a lead cation by the bark leads to the release of two H+. This seems to show that the removal of lead could be interpreted as an ion exchange with hydrogen belonging to the hydroxyl groups of the modified bark.

Jan 1, 1994

By James J. Komadina, Robert R. Beebe

"Heap leaching of gold ores has enjoyed wide acceptance in the arid and semi-arid regions of the western U.S., Australia and South America. There are areas, however, where cold weather or excessive precipitation can limit the usefulness of heap leaching. Even in Nevada difficulties can be encountered which call for special operating procedures.The paper discusses the general climatological limitations and some of the techniques used to extend heap leaching into colder conditions. A case history of the Cripple Creek and Victor Gold Mining Company operation in Colorado examines 'valley-fill"" technology as an ideal cold-climate solution, where topographical conditions permit.AcknowledgementsThe authors gratefully acknowledge the management of Independence Mining Company for their permission to present this paper. The contributions of Golder Associates; Pikes Peak Mining Company Environmental Affairs Department staff, and the Colorado Department of Mines and Geology were all invaluable in successfully concluding this project.BackgroundWhen heap leaching of oxidized gold ores was introduced in the rnid-1970s it was aimed at large tonnages of low-grade material which could not, in general, be developed via conventional milling. Normally, the reasons for this were economic rather than technical: capital and operating costs for milling were simply too high. At first, grade was almost the only criterion, but deposits too small to justify milling were also potential targets for heap leaching.Renewed interest in gold was centered in the western United States and Australia, where exploration for milling-grade deposits had never really died. When heap leaching came along, it was in these areas that the first developments took place. Coincidentally, these same areas were favorable for heap leaching: climates were temperate for most of the year and competing land uses were limited. Even so, in the western United States in particular, winter temperatures were low enough to complicate operations. Precipitation was less a problem, although heavy snowfalls could periodically interfere as well."

Jan 1, 1997

By Frederic Pineau

Semisolid metal alloys have a special microstructure of globular grains suspended in a liquid metal matrix. This particular physical state of the matter can be exploited to produce near-net- shape parts with improved mechanical properties. However, the behavior of the slurry is strongly influenced by the local solid fraction and state of agglomeration. Different flow instabilities ·associated with the combined flow and solidification process result, which make difficult the application of semi-solid processing in the casting industry. Moreover, the rheology of semisolid materials is not well understood. Most of the theory has been derived from experimental data, which are somewhat difficult to measure. A model that accounts for the multiphase nature of semisolid slurries is required to get more insight into such complex flows. This paper describes a mixture model for semisolid slurries. It assumes that the mixture of liquid-solid components behaves as a single fluid as far as overall mass and momentum balances are concerned. The coupling force between the phases is derived on the assumption that the slurry is a fluid saturated isotropic media. The proposed methodology is implemented in a finite element code. The model is then applied to the the filling of an industrial-scale capillary flow viscometer. Segregation patterns are obtained and discussed.

Jan 1, 2001

By Thomas P. Battle

Titanium is the ninth most common element in the Earth's crust, yet only in this century has titanium come into use as an engineering material, particularly in aircraft structures, as the metal, and in pigments, as the dioxide. In this presentation, the metallurgical aspects of processing titanium-containing raw materials will be reviewed. Particular emphasis will be given to the ores and beneficiation techniques which lead to the production of titanium dioxide pigment, which accounts for over 90% of world titanium production.

Jan 1, 1993

By Cang Daqiang, Bai Hao, Li Ning, Liu Xueting, Lu Xin, Zhao Lihua, Li Hongxu, Wei Wei

"Based on the principle of carbon balance, a model was built to calculate C02 emissions of each process and correspondingly the total course of production in iron and steel making. The data from a typical integrated steelworks in China was applied in the model. The results show that the BF and coking process account for the most emissions. Generally, C02 emissions in integrated steelworks depend on three factors, resources utilization efficiency, energy utilization efficiency and energy consumption structure, which were considered in an equation in this paper. Especially, General Emission Factor (GEF) was proposed to assess the relationship between C02 emissions and energy consumption. The results show that, higher GEF will result in more C02 emissions with the same energy consumption and in iron and steel making, the optimization of energy structure and development of eco-industrial park both have significant benefit on the carbon reduction.IntroductionThe Global Warming resulting from the increase of Greenhouse Gases (GHGs), especially C02, in the atmosphere has become the main reason of global climate change, and the carbon reduction is one of the most important ways for the sustainable development [1]. The iron and steel making is a manufacturing industry based on iron-coal high temperature chemical process, in which plenty of C02 is emitted. According to the data from IPCC (Intergovernmental Panel on Climate Change) in 2001, iron and steel making emitted about 650 million tons ofC02 every year, which is the fourth largest industry of the fossil energy consumption [2]. According to the data from EEA (European Enviromnent Agency) in 2006, iron and steel making is the largest source ofC02 emissions, which accounted for about 18% of the total C02 emissions in European manufacturing industry [3].It is estimated that the application of various well developed energy-saving technology, such as Coke Dry Quenching (CDQ), Top Pressure Recovery Turbine (TRT) and Coal Moisture Control (CMC), can make the C02 emissions reduced by 0.5%-3% in iron and steel making, and the further C02 emissions reduction can be achieved if more new energy saving technology is applied, such as sintering plant heat recovery, electricity generation with steam generated from converter and the various by-products gas and the hydrogen making process from COG[4,5]. In addition, the application of membrane separation technology is well expected in iron and steel making [6]. For example, the application of C02 Capture and Storage (CCS) in blast furnace combined with the Pure Oxygen Top Gas Recycled BF (TGRBF) technology can reduce the C02 ennss10ns greatly by about 50%-60% [4].That is, as a kind of C02 end-treatment technology, CCS applied with other technology of C02 recovery would be more meaningful. Actually, reduction of the C02 emissions by changing the structure of energy consumption and raw materials with new process of iron and steel making, such as direct reduction process or smelting reduction process [4,7,8], is the trend of ferrous metallurgical engineering, which is regarded as a kind of source-treatment technology. In this sense, source-treatment technology is more pivotal for the solution of carbon reduction in the future than the current popular energy saving technology. Hence, it is necessary to build the C02 emissions model based on the iron and steel making process and evaluate the relationship between the energy saving and C02 emission reduction."

Jan 1, 2012

By Jun Li, Lin Chen, Tian-zu Yang, Wei-feng Liu, Wan-da Bin

"The Chinese bismuth production accounts for more than 80% all over the world in 2011. The main raw materials of bismuth smelting are bismuth concentrate and by-products of Cu or Pb smelting process. Many traditional methods of bismuth smelting in china was reviewed in this paper, such as reverberating furnace smelting, blast furnace smelting, fire-refining, ferric chloride leaching-hydrolysis, slurry electrolysis, and so on. But all the traditional pyrometallurgy or hydrometallurgy process have such shortages of low recovery, poor environment, and high cost. Therefore new technologies are introduced into the smelting process of bismuth concentrate, such as low-temperature alkaline smelting and side-blown bath smelting with oxygen-enrichment. These technologies have got great progress on energy saving, emission reduction, and friendly environment. Finally the development direction of new technology on bismuth smelting was prospected.IntroductionAs a green metal, bismuth has a wider applications, just extending from the traditional medicine, metallurgical-chemical engineering, low-melting alloys, solders, catalyst, and electronics to cosmetics, flame retardant, storage battery, semiconductor, supper conductor and nuclear energy etc[1,2,3,4,5,6,7]. This will increase the production of bismuth and promote the development and progress of bismuth smelting technology. At present, The major bismuth-product countries are China, Mexico, Peru, KZ, Bolivia and Canada etc, and China are dominating. A survey from the USGS[8] showed that Chinese bismuth production were 12,500 tonnes and got 80% of the world's in 2011. Thus the technology of Chinese bismuth smelting have a great representativeness."

Jan 1, 2013

By P. C. Chaubal

The overall kinetics of oxidation of single partic1es of chalcopyrite have been studied for temperatures up to 1273 K. The experiments were conducted in a stationary bed reactor using a non-isothermal technique. Any mass and heat transfer effects on the kinetics of oxidation were eliminated by using a high-enough gas flowrate. Up to temperatures of 873 K, pore-bl1ocking kinetics were applicable, whereas above 873 K, power-law kinetics gave a satisfactory fit of the data. The activation energy was 215 kJ/mol below 754 Kand 23.7 kJ/mol above 1,060 K. Predominance area diagrams were constructed at various temperatures and used in conjunction with X-ray analyses of partially oxidized samples to determine the intermediate phases formed during the reaction. The analysi1s also provides a justification for the kinetic models used. The results indicate that the reaction rate is first order with respect to oxygen concentration and inversely proportional to the square of the particle size throughout the ranges of temperature studied.

Jan 1, 1985

By Rune Gammelsmter

Turbulent chemically reacting flows are generally very complex, involving interactions of chemical, thermodynamic, and fluid mechanical processes. A combustion model based oh algebraic moment closure has been developed. The model is applicable for reaction rates where the chemical kinetics can vary from slow to fast. The effects of turbulence is taken into account by means of modifications to the well known k-e modelling procedure. The model is applied to an industrial combustion process. Calculation of furnace off-gas combustion from an aluminum reduction cell has been performed. The theoretical results agree well with experimental values.

Jan 1, 1992

By R. G. Reddy

The Margules .equation is used for interpreting excess Gibbs energy of several ternary systems. In the present study activity coefficient of 'a dilute solute, 2, in a binary solvent 1-3 was derived. The derived expression is used to interpret logarithmic activity coefficient of oxygen and sulfur in several metallic systems. Self interaction parameter of the solute is derived from the partial function of solute using constant compositional path. An expression for logarithmic activity coefficient and self - interaction parameter of solute is also derived using Maclaurin infinite series. The derived equation is based on Maclaurin infinite series used successfully to deduce thermodynamics of self interaction of oxygen as a interstitial atom in two metallic systems. The predicted thermodynamic parameters values using Maclaurin infinite series and Margules. equations, are in excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.

Jan 1, 1996

By B. C. Blakey

The economic feasibility of the sulphuric acid pressure leaching route for the extraction of nickel and cobalt values from limonitic ores is highly dependent upon the behavior of aqueous aluminium. This is primarily due to its precipitation as hydronium alunite ((H30)A13(S04)2(OH)6), which is one of the major scale-forming compounds found in autoclaves used for pressure leaching. As a result of renewed interest in the pressure leaching process, an investigation of the aqueous-solid eqilibria in the aluminium-sulphate-water system under acidic (< pH l), high temperature (230 to 270°C) conditions has been conducted. Pure hydronium alunite was synthesized in an autoclave by leaching boehmite (A100H) at elevated temperatures in sulphuric acid solutions initially 0.25 to 0.75 m H2S04 in concentration. Spontaneous, in situ precipitation of hydronium alunite followed. A high temperature solution speciation model was used for the analysis of the resulting solubility data in order to calculate equilibrium constants for the precipitation reaction.

Jan 1, 1994

By Robin M. Forbes. Jones, Suhas V. Patankar, Ramesh S. Minisandram, Jr. Carter, Kanchan M. Kelkar

"The nucleated casting process currently under development has the potential for production of Ni-base superalloy preforms that possess superior microstructure to product made by conventional casting processes, primarily for gas turbine applications. In this process, electroslag remelted (ESR) clean (i.e., free of ceramic inclusions) molten metal is conveyed via a watercooled copper Cold-walled Induction Guide (CIG) to a gas atomizer. The spray of clean metal droplets is then directly cast into a water-cooled crucible for ingot production. The microstructure of the resulting ingot preform evolves within the length scale of the individual droplets and is a function of the thermal state of the incoming metal droplets. This, in turn, depends on particle size, flight time and heat exchange with the gas phase.In the present study, computational models is developed for the analysis of the flow and heat transfer in the gas-metal spray system under axisymmetric and steady-state conditions. The gasphase flow is analyzed using an Eulerian framework and turbulent mixing within the gas phase is modeled using the two-equation k-e model. The dynamics of the metal particles is analyzed using a Lagrangian framework that involves calculation of the trajectories of the metal droplets. A two-way coupling is considered whereby the transport and heat transfer in the gas and the metal phases influence each other.The analysis is developed at two levels. The spray model performs a detailed calculation of the spray dynamics in the vicinity of the spray and is intended for predicting the temperature and mass flux distributions of the metal spray depositing into the mold. The chamber model enables prediction of gas flow and motion of metal particles in the entire spray chamber."

Jan 1, 2004

By René Winand

The paper gives a synthesis of research work performed in the department during the last ten years and dealing with cobalt , copper and manganese electrodeposition in chloride aqueous solutions. Special emphasis is given to electrocrystallization. For copper, properties of the electrolyte such as solubility limits, electrical conductivity and complex ions stability are discussed in connection with leaching, purification of the electrolyte, and metal recovery. When possible, kinetic parameters and probable electrode mechanisms are given. Problems that are still to be solved are also listed.

Jan 1, 1985

By Lætitia H. Delmau

SXFIT is the latest in a series of programs developed in our group to model solvent extraction systems of increasing complexity. SXFIT permits the user complete freedom to define the constituents from which the composition of each phase is to be specified in the data and from which all species of a model for a system are assumed to be formed. Activity coefficients in the nonaqueous and aqueous phases, water activity, apparent molar volumes of aqueous species, and solution density needed for the conversion of concentration from the molarity to the molarity scale are all taken into account by the program. Several extraction systems relevant to nuclear-waste treatment were modeled successfully using this program. As an example, the cesium extraction efficiency of the CSSX process chosen by the USDOE for cesium removal from high-level waste stored at the Savannah River Site can be predicted correctly for varying feed composition.

Jan 1, 2003

By Cody Burcher-Jones

The recovery of rare earth elements (REEs) through heap leach/in situ techniques from so-called ion adsorption clays (IACs) is attractive due to their inherent simplicity. However, the underlying mechanisms of these processes are poorly understood. In this study, the deportment of REEs in a typical IAC material has been investigated and was found to concentrate in the phyllo-layers of the clays, especially hallyosite, and was readily desorbed by various ion-exchange reagents indicating various potential routes to liberate them. Here we are reporting the use of seawater (0.5 M NaCl), spiked with various amounts of (NH4)2SO4, and found better extraction using a reagent mixture than NaCl on its own. Further, the leaching of REEs from a bed of clay material was investigated over time to understand the rate of transport through the stagnant material. Results indicate that REE release is likely to be controlled by diffusion through the clay material, while desorption in agitated systems is rapid. A degree of fractionation between different REEs can be observed during diffusion. Nonetheless, the successful operation of in situ leach operations for this type of material would depend primarily on how easily solution cocktails can be made to flow through the bed material.

By David G. Dixon

A mathematical model is derived in dimensionless form which simulates the effluent concentration response of reagents from spent heaps under both fresh and recycled water rinsing. The model is based on dispersion from isochoric pathways distributed in length and cross-section, oriented normal to convection channels in ideal plug flow. The effects of heap height, rinsate flow, and initial reagent concentration are examined. It is shown that the rinsing cycle undergoes a distinct shift between fast and slow rinsing at a certain time depending on the amount of stagnant solution in the heap, and the distribution of dispersion pathways. Results of preliminary column rinsing tests on both agglomerated and unagglomerated ores are presented which partially validate the model.

Jan 1, 1994

By KNona Liddell

Many metal recovery processes Involve heterogeneous reactions In porous media accompanied by fluid flow and mass transfer. Modeling such systems Is difficult because of the number of rate processes Involved and is complicated even further by effects due to the structure of the porous medium. Data on even bulk properties of the medium are often severely limited or unavailable. For many such systems, a cell model may provide, an attractive alternative to models based on transport ,mechanisms in a differential volume. A cell model requires less input data and is computationally efficient. Identical residence time distributions can be obtained with models of both types, and both allow conversion and concentration profiles and histories to be calculated. The formulation and properties of cell models for metals recovery are described in detail.

Jan 1, 1996

By Nikhil Dhawan

Electronic waste (e-waste) is a collective name given to discarded electronic devices such as Television, Cellular Phones and Personal Computers. Among the heterogeneous metals present in the e-waste are the base metals: copper, aluminium, nickel, tin, zinc, iron and precious metals: gold, silver, palladium, platinum apart from several hazardous and halogens metals. Hence there is a need to recover these metals from electronic scrap by recycling and then re-use, which can meet large amount of metals demand. Hydrometallurgical processing was employed for the recovery of metals from television printed circuit board (TV PCB). Different lixiviants such as hydrochloric acid, Sulphuric acid, and nitric acid were used to understand the dissolution behavior of copper, iron and lead present in the TV PCB. Effect of increasing concentration of nitric acid was also studied. Selective recovery of tin over 95% in the form of tin oxide was precipitated. The precipitated tin oxide was identified by X-ray diffraction technique. Tin oxide of purity more than 99.9% was obtained.

Jan 1, 2009

By Y. Fukunaka, M. Niinae, E. Kusaka, T. Kuzuya, R. Ishii

"Samarium oxalattr particles was precipitated in oxalic acid aqueous solution from samarium-loaded D2EHPA solution emulsified with a conventional impeller. The calculated fractional precipitation of samarium oxalate was reasonably compared with the value determined by chemical analysis. Morphological variation of oxalate precipitate particles was then examined with H2C2O4 concentration in aqueous solution, Sm(III) and D2EHPA concentrations in organic phase. The needle-like precipitate was identified as Sm2(C2O4)3 10H2O by XRD. Precipitates obtained at higher H2C2O4· or Sm(III) concentration greatly decreased the length of major axis of precipitate, while those at higher D2EHPA concentration increased it. The oxalate was further precipitated under ultrasonic irradiation. However, the morphological variation caused by theses processing variables was not so evident under ultrasonic irradiation as in an impeller or shaking mixer.IntroductionThe materials processing of the rare earth elements must be reviewed from the scope of industrial ecology, since they have the potential applications of magnetic materials as well as secondary battery in developing programs of the electric vehicle. The technological trend to develop the electric vehicle may greatly influence the concept of materials processing, since the global· environmental problem must accommodate with the sustainable development for mankind. The recycle design must be a key issue in the materials science and engineering.Solvent extraction provides a unique separation technology -in this sense. Doyle (1)(2) reported the integrating solvent extraction with processing of advanced ceramic materials, whose chemical composition and microstructure must be precisely controlled. In her paper, the higher productivity inherent to the present process superior to hydrolyzing metal alkoxides was emphasized. Oxalic acid has been used as precipitant for rare earth purification process, since rare earth oxalate has a very small solubility in water and can be easily decomposed to oxide. It is thus suitable for precipitation stripping agent in cationic exchange type extracting system (i.e. D2EHPA, VA-10, PC-88A and so on)."

Jan 1, 2000