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By Guy L. Fredrickson

A modified transpiration reactor was used to measure the composition of the equilibrium gas phase formed above compounds in the Hg-O-S system at high temperatures (600 to 900K). A thermodynamic database {(AGo°f AH°t. AS°t)} for-HgO, HgS, HgSO4, Hg2SO4, HgSO4?HgO, and HgSO4?2HgO was developed based on the experimental results. Prior to this study, only estimated data were available in the literature for the sulfates and oxysulfates at temperatures above 298K. A series of vapor pressure' stability diagrams were constructed from 473 to 973K with isobars of Hg(g), HgO(g), S2(g), and SO3(g). These diagrams were found to be significantly different than those available previously and do provide insight to the phase relations of importance during the thermal processing of Hg-containing wastes. The thermodynamic results were used to conduct a series of Gibbs energy minimization calculations for a thermal processor' afterburner system for the treatment of HgS-containing wastes. The retention of Hg in the discharge calcine was examined as a function of temperature and excess air. Hg was found to report to the calcine as HgSO4, Hg2SO4, or HgSO4 HgO depending on the process conditions, and Hg retention occurs at temperatures as high as 930K. The precipitation of Hg-containing phases from cooled afterburner discharge gas starts at approximately 900K and the cooling of the gas an additional 30K (to 870K) results in over 50% of the Hg being preCipitated as HgS04?HgO. It was also determined that for small amounts of Hg present in sulfide concentrates during roasting, the Hg will be retained as HgSO4 or HgSO4?HgO at temperatures as high as 870K.

Jan 1, 1996

By Rina Kim

The addition of lead to a gold leaching reactor can effectively accelerate or retard the gold cyanidation reaction. This study explored the effect of lead on the gold dissolution kinetics using cyclic voltammetry (CV) experiments. It was illustrated that the gold leaching kinetics in the cyanide solution enhanced with the addition of lead salt in the low overpotential region (–0.35 V vs. Ag/AgCl). The similar behavior was observed in the presence of ore containing 0.25% galena. In contrast, the gold oxidation kinetics retarded at –0.35 V (vs. Ag/AgCl) in the presence of silicate and lead-bearing mineral under certain conditions. Likewise, the lead addition was not functional for the high sulfur ore. This was attributed to the oxidation of the sulfides to the elemental sulfur, which subsequently formed a passivating layer on the gold surface. The results were evidently affirmed by the electrochemical tests and X-ray photoelectron spectroscopy (XPS) analysis.

By S. R. Reddy, 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.1 IntroductionIn most of the pyrometallurgical high temperatures processes, interactions of solutes such as oxygen, nitrogen and sulfur, with the solvent atoms are most important during refining processes. There are numerous theories are developed [1-25] to interpret the thermodynamics of solutes in multicomponent alloy systems. Which are mainly developed using statistical or Quasichemical equations.Wagner [4] developed one energy parameter ideal solvent model based on activity coefficient of solutes compositional dependency. He used one energy interaction term which is not able to account for interaction energy parameters for the same solute concentration at different solvent compositions and also it is ineffective model to predict for strong interacting systems."

Jan 1, 1996

By Takahiro Miki

In order to use metallurgical grade silicon (MG-Si) as a starting material for solar cell, phosphorus has to be removed from silicon because phosphorus is a n-type dopant. On the other hand, silicon, ferrosilicon, and silicomanganese are widely used as deoxidizers in steel refining processes. Since most of the phosphorus introduced during the deoxidation process is brought into final products, it is important -to lower the phosphorus content of these alloys. Hence, thermodynamics of phosphorus in such metals is important for the evaluation of dephosphorization processes. In the present study, thermodynamic properties of phosphorus in molten Si-P alloys at 1723- 1848K and those of Si-Fe-P and Si-Mn-P alloys at 1723K have been determined by equilibrating respective metals in a controlled phosphorus partial pressure. The results are expressed as follows.

Jan 1, 1998

By Young-Dae Kim, Dong-Sic Kim, Jong-Jin Pak, Kyung-Hyo Do

"Sulfur is one of the most harmful elements in stainless steel (SIS) products and the specification of sulfur content is getting more severe for high grade SIS. In order to accurately control the desulfurization reaction in high chromium containing SIS melts, it is important to know the thermodynamic interaction between chromium and sulfur in Fe-Cr melts over a wide range of chromium content. In this study, the equilibrium sulfur distribution, Ls, between a Ca0-Alz03 slag and Fe-Cr-C,.,-S melts were measured under CO atmosphere in the temperature range of 1823-1923 K. The specific effect of chromium on the activity coefficient of sulfur in the melts was determined with the consideration of carbon effect on sulfur. A separate experiment was carried to determine. Ls between a slag and FeCr- S melts (Cr: 0-30 mass%) at 1873K to check the validity of the thermodynamic parameter determined in the present study.IntroductionFerritic stainless steels containing chromium (Cr) up to 30 mass% have been developed for a good corrosion resistance and a high formability to replace austenitic SIS. Especially, Sulfur (S) causes a reduction of high-temperature strength and the hydrogen induced cracking (HlC) in stainless steel for line pipes. [l]Many studies on the desulfurization of hot metal and liquid steel have been carried out for several decades and they used HzS-H2 gas equilibrium technique for measuring the effects of many alloying elements on the activity coefficient of S in liquid iron. However, the study on desulfurization of Fe-Cr melts was very scarce.[2] In order to accurately control the desulfurization reaction of high Cr stainless steel, it is essential to know the thermodynamic relation between Cr and S in Fe-Cr melt over a wide range of Cr content and temperature.In the present study, the thermodynamic interaction between Cr and S in liquid iron was determined by measuring the equilibrium distribution ratios of S between Fe-Cr-C,.1-S melts containing a wide range of Cr up to 30 mass% and a 55 mass%Ca0-45 mass%Alz03 slag of which the sulfide capacity was pre-determined using Fe-C,a1-S melts in the temperature range of 1823-1923 K. The validity of thermodynamic parameter determined in the present study was checked by measuring the S distribution between a Ca0-Alz03-Mg0 slag of known sulfide capacity and liquid Fe-Cr-S alloy at 1873 K. Using Wagner's formalism, the results of experiment were thermodynamically considered to determine the effect of a specific concentration of Cr on the activity coefficient of S in liquid iron."

Jan 1, 2014

By Mônica Suede Santos Silva

This work describes characterization of the performance of the tundish of a six strand continuous casting unit of the Companhia Siderurgica Belgo Mineira, Joao Monlevade, Brazil using physical modeling. Permanent and transient conditions, due to ladle metal composition changes are considered. Pulse and step tracer addition techniques are employed to assess the control variables. For transient conditions the degree of inter-mixing and the minimum residence time are determined with a view to optimize the process especially during the grade changes of steel.

Jan 1, 2003

By A. Christlo

Short circuit detection in 1984 involved nine inspectors for production rates of 43,000 tpa. Trials indicated the feasibility of applying cell voltage monitoring to short circuit detection and improving operational efficiency. A computerised cell voltage monitoring system was commissioned in February 1986, to read voltages from 648 cells. The system incorporates 16 evenly distributed work face units which communicate with a central computer system. Provision has been made in the computer program for the automatic adjustment of cell reference voltages. This allows for the effect of polarization and other process variables which might other wise interfere with short circuit detection. The work face units can continue to work independently for several days should this become necssary. Current efficiencies have been maintained and the number of inspectors reduced from nine to five.

Jan 1, 1987

By Faustino G. Prado

In the, quest for an economical and environmentally friendly reclamation of metallurgical dusts generated during pyrometallurgical operations, our goal has been the separation and recovery of most of the components, as well as the complete recycle of all the reagents. Effluents have been avoided, within acceptable economic parameters. This presentation, which can be applied to a large spectrum of dusts and other residual-materials-, has focused on the dusts generated by the operation of Secondary Copper Smelters. Those dusts show a wide range of components, including zinc, lead-, copper, cadmium, tin, chlorine and-alkalies. Our present work deals with the use of ammonium salts in the separation and recovery of-the above mentioned elements in a marketable form. Most of the chemistry and techniques involved have teen already confirmed in commercial scale operations. Others have gone through pilot scale tests or bench scale tests. The recycle of reagents has also been- confirmed at the same operating levels. A preliminary evaluation indicates that the chosen route, in addition to a viable economy, offers a complete and safe reclamation within the most strict environmental regulations.

Jan 1, 1995

By D. Lui, B. G. Thomas, B. Ho

"Results from mathematical models and plant experiments are combined to quantify the effect of transverse depressions and oscillation marks on heat transfer in the continuous casting mold. A heat transfer model has been developed to calculate transient heat conduction within the solidifying steel, coupled with the steady-state heat conduction with the continuous casting mold wall. The model features a detailed treatment of the interfacial gap between the shell and mold, including mass and momentum balances on the solid and liquid powder layers. The model predicts the solidified shell thickness down the mold, temperature in the mold and shell, thickness of the resolidified and liquid powder layers, heat flux distribution down the mold, mold water temperature rise, ideal taper of the mold walls, and other related phenomena. The important effect of non-uniform distribution of superheat is incorporated using the results from previous 3-D turbulent fluid flow calculations within the liquid cavity. Results from plant experiments confirm that transverse surface depressions and oscillation marks form at the meniscus and move down the mold. Measurements of mold thermocouple temperatures and breakout shell thickness were used to calibrate the models. The results indicate that the surface depressions and oscillation marks are filled with mold flux, but still have a significant effect on decreasing heat transfer. The predicted mold temperature fluctuations are consistent with measurements. If the depressions become filled with air, their effect is greatly increased. These results should be useful in the difficult task of interpreting transient mold thermocouple signals for on-line quality monitoring.IntroductionMany different types of intermittent surface defects on steel slabs arise during initial solidification in the mold of the. continuous casting machine. These defects include deep oscillation marks, surface depressions, and cracks. They may lead to quality problems, such as slivers, in the final rolled product. In severe cases, breakouts may occur, where liquid steel bursts through a thin section of the shell and drains over the casting machine below the mold."

Jan 1, 1997

By Jorge A. S. Tenorio, Chuanwei Zhuo, Joner O. Alves, Yiannis A. Levendis

"Reduction of combustion-emitted greenhouse gases, which are associated with global warming, may be achieved by use of CO2-neutral alternative fuels, such as bio-ethanol. Distillers Dried Grains with Solubles (DDGS) are the main co-products of the com-grain-based ethanol industries. In 2009, the North American production of ethanol from com was about 38 billion liters, which generated approximately 31.5 million tons of DDGS. Samples of DDGS were pyrolysed at temperatures of 600-1000 °C in a two-stage laminar-flow horizontal furnace, and a catalyst system was used to synthesize nanomaterials. This work presents a microstructural characterization of these nanomaterials by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Results showed that the nanomaterials produced from pyrolysis of DDGS were in the form of long, entangled, rope-like structures with rugged walls, lengths in the tens of microns, and axially non-uniform diameters in the range of 100-300 nm.IntroductionThe interest in ethanol has increased considerably worldwide due to the necessity of finding renewable and cleaner energy resources [1, 2]. According to the Renewable Fuels Association (RF A), the world ethanol production in 2008 was approximately 65.7 billion liters (17.3 billion gallons), which figure represented a 24% increase in the production over that in the previous year [3]. The major producers of ethanol are the USA and Brazil, which together account for 90% of world production. The main feedstock for ethanol in USA is com grain, whereas sugarcane predominates in Brazil [2-4]."

Jan 1, 2011

By Tuula Mäkinen

One of the latest applications of the Outokumpu Flash Smelting Technology is the direct smelting ,of nickel concentrates to metallised low-iron nickel mattes. Compared to the conventional nickel smelting, the new DON process needs a lower number of smelting vessels resulting in considerable economic and environmental benefits. Fundamentals of smelting nickel concentrates in one stage to low-iron mattes are presented. Properties of nickel. smelting slags with an emphasis of the slag fluidity at high MgO-levels are also discussed. Conditions prevailing in DON mattes at high oxidation degrees are presented as well as their influence on the behaviour of such mattes in the settler and on tapping the furnace. Distributions of elements in the direct smelting are presented and compared with the conventional process. A further comparison is made with pilot-plant data and the industrial scale.

Jan 1, 1998

By Rina Kim

There are many factors which affect the gold cyanidation mechanism— mineral composition, free cyanide and dissolved oxygen (DO) concentrations, heavy metal additions, etc. This study combines electrochemistry and surface analysis methods to examine the effectiveness of the above factors on gold cyanidation process. Three gold ore samples were used in this study. Sample 1 was a pyrite concentrate, contained mercury and silver. Sample 2 also contained sulfide minerals, including galena. Sample 3 contained pyrite with sphalerite and galena. In the case of samples 1 and 2, the presence of heavy metals enhanced gold cyanidation kinetics, though the addition of higher DO was not effective on improving the kinetics. Sample 3 showed an opposite behavior: the kinetics was not enhanced by galena, because of its relatively small amount, however, the use of higher DO made improvement in the gold leaching kinetics, likely caused by iron species generated by pyrite oxidation.

By I. Mc Dougall

"The matte/slag tidal zone in a platinum smelting furnace is subject to severe process conditions which can often lead to premature failure of the lining. The MgO-FeO-Si02 slag is aggressive to refractory bricks, whilst the Ni-Cu-Fe-S matte is aggressive to water-cooled copper cooling elements, and can penetrate and sulphidize refractory bricks, particularly at the high matte temperatures often experienced in the PGM industry. A novel approach to the lining design was taken at Lonmin's new 10MW Furnace 2. An indirectly-cooled graphite ring was applied in the matte/slag tidal zone, with refractory bricks on the hot face. Thermal Finite Element modeling was conducted to determine the optimal lining design in this region of the furnace. The resistance of two graphite grades to damage by slag and matte was evaluated experimentally. The graphite lining is not wet by the matte, and is resistant to slag attack at operating temperatures. In comparison to water-cooled copper in various configurations, cooled graphite shows promise as an indirect refractory cooling system in the tidal zone area of furnaces.IntroductionIn South African Platinum Group Metals (PGM) smelting operations, the PGMs are associated with nickel-copper sulphides in magmatic rocks. After ore is mined, it is concentrated by means of a flotation process prior to smelting. Both rectangular 6-in-line and circular 3 electrode AC submerged arc furnaces are used for this purpose. A new 10 MW round furnace is currently under construction by Tenova Pyromet at Lonmin's Marikana Smelter Division. An overview of Lonmin's smelting operations and Lonmin's approach to smelting high chromite containing PGM concentrates is given by Eksteen et al. [1]"

Jan 1, 2012

By Nicholas Zabaras, Deep Samanta

"Solidification of metal aluminum and aluminum alloys is modeled on uneven surfaces characterized by sinusoidal curves. Wavelengths and amplitudes of these sinusoidal surfaces are varied to study their effects on processes like solidification, macro-segregation and inverse segregation. Solidification and macro-segregation are modeled using a slightly modified form of a stabilized finite element method developed recently to model high Rayleigh number solidification and porous media flows. For pure metal solidification, the effect of varying amplitudes and wavelengths is observed in heat transfer, fluid-flow ~nd phase change processes. The relative importance of shrinkage driven flow and solutal convection on the redistribution of solute for an alloy solidifying in a rectangular cavity is compared. The analysis is then extended by modifying one of the surfaces to a sinusoid. In this case the effects of varying amplitudes and wavelengths are studied in heat transfer, fluid flow, phase change, macro-segregation and inverse segregation processes.1 IntroductionTransport phenomenon during solidification of alloys is a major cause ofcasting defects such as segregation, micro-voids, hot tears, porosity, internal and surface cracks. Heat flow across metal and mold surfaces directly affects the phase change process and plays an important role in determining freezing conditions within the metal. In alloys, natural convection and shrinkage play an important role in determining the final solute redistribution, macrosegregation and evolution of solid macromorphology. Surface unevenness plays an important role during the early stages of solidification. It influences the heat transfer rate and fluid flow in the melt, which in turn affect the morphology and shape of the solid-liquid interface. The effect of surface unevenness on solute redistribution is important during solidification of alloys, where solute driven flow in the mushy zone is prominent. Thevik and Mo in [7] and [8] used a one dimensional model for studying surface segregation and macrosegregation in alloys under the influence of exudation and solidification shrinkage. Air-gap formation in their model was expressed through a variable convective heat transfer coefficient at the boundary. Tsai et al. in [3] and [4] have modeled macrosegregation in an aluminum-copper alloy driven by shrinkage and solutal convection. They used a single domain model based on mixture theory and solved the transport equations using finite difference methods. Our aim is to model solidification of aluminum followed by macrosegregation and inverse segregation in aluminum-copper alloys on uneven surfaces by finite element methods. These surfaces are modeled as sinusoids characterized by amplitudes, ?s and wavelengths, As, By varying As and ?s, changes in heat transfer, fluid flow, phase-change and macrosegregation are studied."

Jan 1, 2004

By Yoichi Takeda

Copper solubility in SiO2-CaO-FeOx slag equilibrated with copper matte in 10% SO2 atmosphere at 1573K was estimated. Essential parameters are activity coefficients of copper oxide and sulfide, oxygen and sulfur potentials and activity of copper in the slag-matte system. A large number of experiments provide proper parameters to calculate copper solubility in slag, A classical thcrmodynamic model postulating CuO0.5 and CuS0.5 moleculcs assists in estimating copper solubility in slag. Additions of Si02 and CaO reduce copper solubility almost in any condition. Copper loss, that is function copper solubility and slag volume, in the silica saturated SiO2-FeO. binary slag is minimally equilibrated with less than 66% copper matte while copper loss in the 50% FeO.-SiO2-CaO ternary slag saturated with 2CaOSiO2 is minimally equilibrated with over 66% copper matte. This slag composition has potential for continuous copper converting, direct copper production or high-grade matte production.

Jan 1, 2003

By C. A. Silva

Ladle change-over, during continuous casting of steel, initiates transient flow in the tundish which influences the inclusion content and degree of mixing between two consecutive batches of steel. The mixing behavior in the tundish during this period is determined by the casting rate and the ratios of: inflow to outflow during the refilling period; and, the low liquid level relative to the nominal level in the tundish during the transiency. A 3:10 scale water-model of a typical one strand slab caster was operated in conjunction with a tracer technique to characterize the velocity fields for several combinations of these parameters. Steady operation, a limiting case of the transiency, provided a basis for comparison. High-order moments -- skewness and kurtosis -- of the residence time density function have been utilized as signature elements associated with a particular residence-time distribution for the system. A simple mathematical model incorporating the above parameters as well as a characteristic Peclet Number was successful in simulating the features of the transient period.

Jan 1, 1993

By Richard D. Hagni

The mineralogy of dusts from the lead sinter and lead blast furnace at the Doe Run Smelter at Herculaneum, Missouri is being studied by reflected light microscopy and scanning electron microscope-energy dispersive spectroscopic analysis (SEM-EDS). Oust from the sinter plant consi5ts of abundant slag and galena particles, and lesser amounts of coke, sinter, and chalcopyrite particles. In contrast, dust from the blast furnace consist of abundant coke and sinter particles, and lesser amounts of slag, galena, chalcopyrite, metallic lead and lead-copper particles. The particles in dusts from remote sampling sites !-l mile from the sinter plant and blast furnace are fine-grained and composed principally of calcium-aluminum silicates that are locally derived, but some of the larger particles consist of sinter, slag, galena, and other minerals. Additional dust samples from the plant and remote sites are currently being studied.

Jan 1, 1991

By E. Fregeau-Wu

The major obstacle in recycling steelmaking slags to the blast furnace is their phosphorus content. Removal of the phosphorus, which is primarily associated with the silicate and phosphate phases, would allow for greater recycle of these slags for their iron, manganese, and lime contents. Calculations show that separation of the silicates from the oxide phases would remove nearly 90% of the phosphorus from the slag. The variable grain size of the as-received slag made liberation by fine grinding difficult. Therefore, slow-cooling experiments were undertaken to improve the grain size distribution. The grain size distributions were determined using in-situ image analysis. The samples were ground to their apparent liberation size and high gradient magnetic separation was used to separate the magnetic oxides from the nonmagnetic silicates and phosphates. Liberation analysis and modeling was performed on selected separation products for discussion of benefication characteristics.

Jan 1, 1995

By R. Shimpo

Equilibrium calculations by a computer may sometimes fail in giving solutions when the system includes a large number of components and more than three phases, and especially when no definite information about stable phases is given. An improved method of calculation is presented in which the number of phases need not to be initially fixed, phases can appear or disappear in the course of' calculation and a new method is combined with the Newton-Raphson method to obtain solutions easily. The improved method is applied to the copper smelting operation and all the successive stages of the operation are successfully simulated.

Jan 1, 1983

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to predict the distribution behaviors of Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag in copper pyrometallurgical process. In this model, as more as 21 elements (Cu, S, Fe, Ni, Co, Sn, As, Sb, Bi, Pb, Zn, Au, Ag, 0, N, C, H, Ca, Mg, Al, and Si) and 72 compounds (in fayalite-slag-making system) or 74 compounds (in ferrite-slag-making system) are considered. Accessory-element behavior is studied for two types of slag , fayalite and ferrite, and two levels of oxidation. The allowance is also made to account for physical entrainment in the melts.-Model simulations are carried out to study the effects of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxygen enriched air. The model can be used in copper flash process, Mitsubishi process and Noranda process. The predictions by the present computer model are compared with the known industrial data from Gui Xi Smelter in China, Home Smelter in Canada and Naoshima Smelter in Japan and excellent agreement between calculations and industrial data is obtained. In this paper, the effects of oxygen enrichment, matte grade, smelting temperature, and types of slag on accessory-element behavior among matte, slag and gaseous phase have been elucidated.I . IntroductionThe presence of trace quantities of minor elements such as As, Sb and Bi in copper significantly reduces its ductility, electrical conductivity, and lowers its thermal conductivity. Embrittlement of copper also occurs due to impurity-phase precipitates at the copper grain boundary interfaces. They deteriorate not only the electrical conductivity of copper but its workability in hot working."

Jan 1, 1998