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By M. Aushouri, S. H. Mansouri, N. Aminizadeh

A thermo-chemical model of the Peirce-Smith copper converter has been developed to predict the molten temperature. The primary assumption of the model was that all matte, slag and gaseous phases in the converter were in thermal and chemical equilibrium. In this model, the matte components were considered only as copper, iron and sulfur elements. In the slag making stage, all the reacted iron was converted to fayalite. The reaction rate of iron and oxygen in this stage was considered to be constant. The converter temperature was calculated by heat balance over time. The model was validated by a detailed comparison with measured industrial data. A good agreement was obtained. The converter temperature depends on process parameters such as oxygen efficiency and molten emissivity.

Jan 1, 2007

By M. Aushouri, S. H. Mansouri, N. Aminizadeh

A thermo-chemical model of the Peirce-Smith copper converter in blowing the copper stage has been developed to predict the molten temperature. The key assumption of the model was that white metal and gas phases in the converter were in thermal and chemical equilibrium. In this model, the chemical reaction of white metal and oxygen was accomplished completely. So long as sulfur existed in the bath, the generation of Cu2O was frozen. The reaction rate was considered to be constant and controlled by the reacted sulfur. The converter temperature was calculated by heat balances over time. The model was validated by a detailed comparison with measured industrial data. A good agreement was obtained. The converter temperature depended on process parameters such as oxygen efficiency, molten emissivity and oxygen enrichment.

Jan 1, 2007

By M. Abdelkhalek, M. Hepworth, D. Tao, B. K. Parekh

Pre-combustion coal cleaning and post-combustion flue gas desulfurization (FGD) using lime or limestone are the primary methods employed to reduce sulfur dioxide (SO2) emission from coal combustion. These processes generate voluminous pyrite and gypsum solid wastes that are usually landfilled, occupying thousands of acres of land and creating serious land and water pollution problems due to the release of acids and toxic substances. An integrated process has been developed for the combined utilization of gypsum and pyrite wastes by converting them into useful products including lime, sulfur, and direct reduced iron (DRI). The process includes four major steps. The first step is to concentrate pyrite from coal preparation tailings using flotation or gravity separation. The second is the thermal decomposition of pyrite into pyrrhotite and sulfur. This is followed by the reduction of pyrrhotite with carbon in the presence of lime to produce iron and calcium sulfide. The fourth step involves the reaction of calcium sulfide with gypsum to produce lime. The chemical reactions involved in the process were studied using thermogravimetric analysis (TGA) and X-ray diffraction (XRD)techniques. Process variables studied included reaction temperature, time, reactant composition, and purity of reactants.

Jan 1, 2000

By J. Antrekowitsch

Keywords: residues, fluorides, chlorides, zinc, steel mill dust The recyclability of various nonferrous metal wastes often suffers from a relatively high fluorine and chlorine content. Both are inserted in most cases by the use of plastic contaminated scrap and a wide variety of different coatings. These halogens lead to poor product qualities and off gas contamination. Especially the history of zinc recovery from steel mill dusts shows, that the today common hydrometallurgical options are on their limit and therefore are not sufficient in most cases. This thermochemical study should give more information about different pyrometallurgical options, that offer both a chlorine and fluorine reduction and efficient zinc recovery, preferably in one process step. Selective evaporation in different atmospheres and conversion with the use of hydrogen are the main parts in this study. The results combined with the relatively small information available from literature should provide a basis for further investigations in this field.

Jan 1, 2005

By S. Gopalan, J. D. Milshtein, S. N. Basu

Production of syngas is proposed utilizing the W/W03 redox system and employing a solarpowered two-step thermochemical cycle. Three chemical reactions occur in two chambers. Assisted by a solar concentrator, a high temperature reaction reduces W03 powder to metallic tungsten in both chambers. Subsequently, the temperature in one of the chambers is lowered and H2(g) is produced via re-oxidation of the tungsten powder using steam. The temperature in the other chamber is simultaneously lowered to an intermediate temperature and CO(g) is produced via oxidation of the tungsten powder using C02(g)· The gas streams coming out of the two chambers result in the syngas production. A complete thermodynamic analysis of the system is described. The W/W03 redox cycle offers greater gravimetric fuel productivity compared to previously proposed systems, and the entire cycle can be operated below 1273K.

Jan 1, 2013

By B. McFadzean, K. Moller

"The mechanism whereby thiol collectors adsorb onto a mineral surface has been widely studied. Most of these studies examine the mineral surface at equilibrium state and, often, well above monolayer coverage. However, the formation of species at the mineral surface is a complex process that is both kinetically and thermodynamically controlled. In a typical industrial application, the dosage of collector will be around monolayer level. This study uses isothermal titration microcalorimetry to measure the heat evolved during the reaction of sodium ethyl xanthate (SEX) and sodium isobutyl dithiocarbamate (SIBDTC) and their mixtures with galena and chalcopyrite. The sensitivity of the instrument allows heats of reaction of sub-monolayer quantities of thiol collector to be measured.The study found that both the magnitude and kinetics of the reaction between a collector and a mineral surface was dependent on the type of mineral and the type of collector. Proposals are made for the reactions based on literature and the evidence from this investigation. It was found that when collectors were reacted with mixtures of galena and chalcopyrite, that the magnitude of the reaction was lower compared to that measured for the pure minerals alone. This may be due to galvanic interactions between the minerals, resulting in a passivating effect on one or both of the minerals."

Jan 1, 2014

By Chuang Y-Y

A summary is made on the thermodynamic analysis for two of the four ternary systems of the quaternary Cu-Fe-Ni-S. The analysis is being extended to ternary Cu-Fe-S and then to the quaternary. An analysis is already made for the metal ternary but is not reported here. Experiment is being carried out to measure the liquidus surface. of Fe-Ni-S equilbrium with the fcc solid solutions of (Fe, Ni). The presentation at the Symposium will include all the results obtained at the time of presentation.

Jan 1, 1983

By A. Nivala, S. Ulgiati, M. Canino

Mining and processing of bastnaesite ore, (Ln)CO3F, for lanthanides extraction is investigated in this paper. This series of elements proved to be applicable for a wide range of high-tech uses. In spite of the strategic importance of lanthanides, no LCA and energy analyses of their extraction have ever been published. We perform in this paper a Life Cycle Assessment of the Lanthanide production cycle, based on available database and literature data from Mountain Pass mine (USA) and other worldwide mining and processing sites, most of which in China. We investigated three main steps: mining, milling (including transport, grinding and drying), and flotation (for lanthanide chloride extraction). We do not investigate here the separation of pure oxides from lanthanide chloride, a compound which is also marketed as such. The conventional LCA was integrated by means of energy and emergy evaluations, aimed at investigating respectively the global energy cost and the environmental sustainability of the process. Indicators of material intensity, thermodynamic efficiency, and environmental impact (including LCA and ecological footprint impact categories) are calculated and discussed.

Jan 1, 2005

By Jillian Spindura

This work investigates the carbothermic reduction of the complex sulphide mineral, pentlandite, in the presence of lime. The effects of change in temperature and the use of different carbon sources are studied and the role of these variables on the reducibility of pentlandite mineral is discussed. The microstructures of the heat-treated pellets are examined using X-ray diffraction and scanning electron microscopic techniques. The latter analytical method also allows any variation in the morphology and composition of the metallic phases formed, with temperature, to be considered. The kinetics of the reduction process is studied and the magnitude of the overall activation energy is determined from the plots of percentage reduction versus time.

Jan 1, 1996

By A Kamaraj, M Mohanasundaram, R Kumar, P Tikare

This study presents a comprehensive thermodynamic optimisation and sustainability analysis of the secondary copper smelting process for Waste Printed Circuit Board (WPCB) recycling. The study investigates various scenarios with different proportions of WPCB in the input stream, ranging from 0 per cent to 100 per cent. Through thermodynamic modelling using FactSage™ version 8.1, the optimisation process is conducted in three stages. The results of the thermodynamic modelling indicate that the best-case scenario for WPCB recycling is achieved with a 40 per cent proportion of WPCB in the input stream. This case exhibits a maximum copper recovery of 99.93 per cent while minimising the formation of other waste. In addition to the thermodynamic analyses, environmental factors such as the carbon emission index and resource utilisation efficiency are studied. The 40 per cent WPCB recycling case exhibits a resource utilisation efficiency of 93.055 per cent and a carbon emission rate of 0.133. The present investigation highlights the significant benefits of a 40 per cent WPCB recycling scenario through a secondary copper smelting process in terms of base metal recovery and energy efficiency, thus emphasising its potential for sustainable PCB waste management and resource utilisation.

Aug 21, 2024

By S. Sridhar, R. E. Aune, M. Hayashi

Thermophysical properties of silicate melts are strongly structure dependent. It is well known that the viscosities of slags increase with increasing the degree of polymerization of silicate anions. Even the thermodynamic properties of slags are dependent on the types of species and the population of the same in the melt. Thus, a link between the thermophysical and thermochemical properties of silicate melts is logically expected. The present paper elucidates the salient features of Darken?s excess stability approach to the Gibbs energies of solutions as applied to the viscosities of silicate melts. It is demonstrated, that the second derivatives of the viscosities of binary silicate melts with respect to composition indicate a maxima corresponding to the existence of stable compounds in these systems. The concept was successfully applied to the following systems: Al2O3-SiO2, CaO-SiO2, FeO-SiO2, MgO-SiO2and MnO-SiO2. In all the cases, the second derivative plots of viscosities with respect to composition showed peaks corresponding to the metasilicates. The second derivatives of the activation energies of viscous flow with respect to temperature has earlier been shown to reflect the formation of associates/embryos in the homogeneous silicate melts, indicating the readiness of the melt to separate a solid phase. Thermodynamic coupling of thermal diffusivities in the case of the system CaO-Al2O3-SiO2from the laser-flash measurements of these slags as a function of temperature are examined as part of the present study. Densities are estimated from integral molar enthalpies in the case of silicate systems and the results are presented. Keywords: silicate melts, viscosity; activation energy, thermal diffusivity; density

Jan 1, 2004

By Pengfu Tan

A thermodynamic model has been developed to predict the distribution behaviors of Cu, Fe, S, O, Pb, Zn, As, and heat balance in a lead blast furnace. The modeling results have been validated by the plant data of a lead smelter in Asia. The model can be used to predict for any set of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxygen-enriched air. The effects of the blast air, industrial oxygen, and coke charge on the distributions of Cu, Fe, S, O, Pb, Zn, As, and heat balance, and on the lead loss in slag have been presented and discussed.

Jan 1, 2005

By Alhondra de los Santos, Jesús L. Valenzuela, Jose R. Parga

"The present study evaluated the feasibility of using iron species generated by electrocoagulation (EC) as an adsorbent for removal As(III/As(V) from aqueous media. The full potential of EC was evident in that more than 99 percent of arsenic was removed without addition of chemical reagents. The adsorbent iron-species generated by EC was characterized by Chemical Analyses, X-Ray Diffraction and Scanning Electron Microscopy. The experimental data were correlated by employing a Langmuir adsorption isotherm. Thermodynamic parameters such as ?H o , ?S o and ?Go were calculated. The adsorption process was found to be exothermic and spontaneous.1. IntroductionArsenic contamination in potable water supplies is a serious health problem in many countries around the world. Groundwater arsenic contamination in La Comarca Lagunera Mexico was first reported 30 years ago [1]. Arsenic concentration has been found in well water from several communities ranging from 0.25 to 1.0 ppm. The elevated concentration of arsenic in water, above that originating from natural sources, has been attributed to the use of organoarsenical pesticides in the cotton fields and also to the millions of tons of waste slag generated at a local lead smelter [1]. The main arsenic species present in natural waters are arsenate ions 3- 4 AsO (oxidation state V) and arsenic ions H3AsO3, - 2 3 H AsO and 2- 3 HAsO oxidation state III). However, As(V) ions are most prevalent in oxygenated water while As(III) is found for anaerobic conditions, such as in well water or in groundwater. Conventional methods of arsenic removal rely on chemical-based treatment with lime, alum coagulation, iron coagulation and chemical oxidation. Other processes used with varying degrees of success include adsorption onto activated carbon, reverse osmosis, nanofiltration, manganese dioxide, magnetite and ionexchange resins [1-3]. These conventional processes generate a considerable quantity of secondary hazardous waste such as solid sludge, which also pose serious environmental problems. These drawbacks have forced various industries to search for effective, alternative treatment technologies for arsenic with a preference for electrochemical methods."

Jan 1, 2008

By Jeffrey R. Taylor

The distribution of low concentrations of Cr, Mn, Rh, Co, Ni, Ag and Fe between copper matte and bullion phases has been measured at 1200oC. These results. together with values for nine other elements, have been used to develop a simple model to describe the distributions in terms of known thermodynamic properties?. The Temkin model for ionic melts was assumed to apply to the sulphide species in the Cu-S matte? phase and it is shown that the choice of sulphide species is particularly important for successful representation of the experimental .results?. In general, the lowest sulphlde (minimum sulphur :. metal ratio)? formed by the. metal is most suitable, although Ni, Co, Rh and Pd appear to associate with more sulphur in the melt than suggested by the? composition of their lowest sulphide. A correlation between the composition of the metal sulphide species formed in the ternary system and the? position of the minimum in the free energy of mixing curve in the metal-sulphur binary -system is? proposed.

Jan 1, 1983

By Yap Chu-Phay

ALTHOUGH chronologically, the Sb-Bi system was the first one studied by the writer, the theoretical basis of the equations used in this paper is fully discussed in the writer's paper on the iron-carbon system,1 because he believed that many would be more interested in the iron-carbon alloys. He suggests, therefore, that the reader consult that paper to familiarize himself with the theoretical aspect of the thermodynamic treatment outlined herein. This paper is divided into two parts: Part I deals with the Sb-Bi system and Part II deals with the lead-rich side of the Sb-Pb system. Although the former system has not much practical interest now, it has great theoretical interest in that it, is the one system that for a long time was thought to have (and under specific conditions still has) an anomalous solidus, which no amount of physical investigation could adequately account -for. The latter system of course, is particularly interesting in the lead-rich end. It will be shown that the thermodynamic method is capable of predicting reliably the equilibrium position of the solidus, and thus acts as a check on the experimentally derived solidus.

Jan 1, 1931

By Yap Chu-Phay

IN 1923, when the writer began his studies in metallurgy, he came upon an article by Professor Honda on the, Equilibrium Diagram of the Iron-carbon System, 1 which made a profound impression on him. What interested him most was this sentence: "In the recent diagram of the iron-carbon system, the solidus is usually shown as a curve bending considerably downward. But it can be shown by thermodynamics that if the liquidus is straight or slightly curved, the same must also be true for the solidus. Hence, in my constitutional diagram, the lower portion of the solidus is slightly bent upward." Ever since then the writer has been interested in thermodynamics, especially chemical thermodynamics. The applications of thermo-dynamics to the metallic systems have been, in the writer's opinion, sadly neglected, although we continually use the phase rule in our study of equilibria in the liquid and solid states of metallic alloys. Many investigators, among whom may be mentioned Heycock and Neville, and s Honda and his coworkers, have applied the simple Raoult-van't Hoff law of depression of freezing point, mainly to determine the heat of fusion, but no attempt has been made to investigate the applicability of the thermo-dynamic laws of solution (as opposed to the laws of solution derived from other sources) to metallic systems" showing either limited or complete solid solutions. Perhaps the reason for this neglect is that until recently there have been so few reliable data on the solidus, which is much more difficult to determine than the liquidus. The writer has under way at the present time an investigation of a number of systems, the solidi of which have been more or less reliably determined. Recently, the writer has not only shown the valid applicability of the thermodynamic laws of solution as applied to the system antimony-bismuth but has also suggested a method of attacking problems involving complete and incomplete equilibria.2 In the present paper, the same method of approach is employed. For convenience, we shall divide this paper into two parts:

Jan 1, 1931

By Edward Saibel

THE various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure, no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3,4 or on the energy required to form new surface.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agreement between calculation and experiment. It has been pointed out by several observers7 that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so - nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory Of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermo- dynamic theory of the tensile strength of isotropic bodies based on work of Born9 relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melt- ing phenomenon, Fürth obtains an expression for the rupture stress u, in the form [ ] where Q is the melting energy per unit mass, ? is the density, and µ is Poissons’ ratio. Fürth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947

By Staia. Mariana H.

Thermochemical equilibria of the heterogeneous system Ti-N-H-CI-Fe-Cr-Mo-Ni-Mn-C were calculated by using a commercial software based on the minimization of the free energy. Equilibrium calculations were done for temperatures varying between 800" and l 100°C and an initial molar relationship between reactants, a=NJTiCI,, of 0.1 to 2. The deposition process was considered to occur at atmospheric pressure. The activities of the alloying elements of the stainless steel were considered equal to their molar fractions. It was shown that for the conditions studied the substrate is no inert with respect to the gaseous phase. The existence of liquid chlorides was predicted for temperatures between 800" and 850°C and a ratio between 0.3 and 0.9. The most important metallic chlorides which appears to be present from the calculations in appreciable quantities in the gaseous phase are iron dichloride and manganese dichloride. In the low-temperatures zone and for low initial nitrogen contents, it result that the appearance of the liquid chlorides seems that partially inhibits the production of gaseous HCI. The highest deposition process efficiency calculated is obtained at a temperature 2 900°C and a N2/TiCI, ratios 2 0.7.

Jan 1, 1995

By Kavetsy A

In surface mining operations, the ease with which a muckpile may be dug is a dominant factor in mining efficiency. Within broad limits this is largely independent of the fragment size dis- tribution, since the equipment used to move the broken rock is generally larger than in underground mines. In such cases, muck- pile shape and voids ratio within a muckpile heavily influence mine productivity. In a particular operation, the muckpile shape after blasting should be tailored to the digging equipment being used. A front- end loader is best suited to a low, flat-lying, loose muckpile, because of its fairly good mobility and small break-out force with its bucket. In contrast, a rope shovel lacks mobility, generates a much larger break-out force with its bucket, and fills its bucket in a vertical filling motion. Therefore, it is ideally suited to well fragmented, steep faces. In situations where a dragline is used, the requirement for a suitable muckpile depends on the operat- ing scheme of the dragline. For a conventional highwall key method the preferred work- ing level of the dragline is the same as the highwall, so that the dragline may sit over its key. In this situation, the ideal muck- pile shape involves relatively little displacement of the fragmented rock, with a minimal "power trough" at the back of the blast. In throw blasting, on the other hand, it is desirable to cast as much of the spoil as possible across the pit. It is then necessary to optimize the blast design by maximizing the throw percentage under any necessary constraints (e.g. damage, vibration, flyrock, explosive cost).

Jan 1, 1988

By James J. Scott

Three dimensional photoelastic techniques have been developed which provide information on the state of stress at any point in a model investigated. This investigation utilizes these techniques to determine the stress distributions in the pillars and the roof of a room and pillar mine model. Castolite plastic was used for the construction of the model in which a stress pattern was developed by the stress freezing process. Analysis of the stress pattern was accomplished by use of data obtained by observing points in slices from the model with a polariscope and solving data obtained by' the shear-difference method. Slices through the centerline, edge of pillar and centerline of span were investigated. Results of this work provide information on the overall stress distribution on points of stress concentration in compression, shear and tension, show relative magnitude of stress throughout the model and indicate directions of the most important stress values. A generalized roof bolt pattern is developed for room and pillar mines based on the stress distribution. A digital computer was used in the reduction of data and proved to be extremely useful for investigation of this type.

Jan 1, 1963