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By Milton Blander

"A review of concepts and theories for predicting thermodynamic solution properties of multicomponent high temperature liquid solutions is reviewed. During the last 50 years the ability to predict such properties for molten salts, silicates and metals based on the generally known properties of the lower order (often binary) systems has been developed and shown to provide predictions which are quite useful in science and technology. There are many gaps in our understanding of these high temperature solutions, especially for metals, and considerably more work is needed.INTRODUCTIONA number of solution theories and concepts have been developed which reliably predict the properties of multicomponent solutions from those of the lower order systems (often only the binaries). Because there is available data for a large fraction of the important binaries, the capability for making predictions for many multicomponent systems used in metallurgical separation processes is broad and potentially very useful. At the very least, the theories greatly minimize the data necessary for predicting properties of complex multicomponent solutions of molten salts, silicates and metals. It is the purpose of this paper to discuss the concepts which are demonstrably useful. We will discuss simple forms of the theories to make the concepts clear but we will refer to the publications which contain the more complex equations needed to treat the large majority of systems.A simple framework for understanding what we need to know in order to make technologically useful predictions is based on well known thermodynamic principles. In technologies and sciences where molten salts, slags magmas or molten metals are used or studied, one must often calculate the extent of a chemical reaction (or separation) or of phase changes. To do this, one must first write an equilibrium constant, K, for the reaction in terms of the standard free energy change of the reaction, ?G°."

Jan 1, 1996

By Fujio Ishii

The deoxidation of liquid nickel and nickel binary alloys with silicon has been determined at temperatures between 1500°C and 1650°C using quartz crucibles in order to investigate the deoxidation of nickel based alloys. The equilibrium constant of the deoxidation reaction in liquid nickel and the effects of the different alloying elements such as chromium, molybdenum, tungsten, iron, cobalt and coppcr on the activity coefficient of oxygen in liquid nickel have been established.

Jan 1, 1993

By F. -Z. Ji

Carbon injection into metallurgical slag is important in electric arc furnace (EAF) steelmaking for foamy slag practices and in nonferrous slag cleaning operations. The current publication presents kinetic data for coal injection into EAF slag to understand the interaction between injected carbon and metallurgical slag. Coal particles were injected into EAF slag and the kinetics were followed by gas and slag analysis. The results were analyzed, in terms of fundamental rate equations for each possible reaction step, as a function of temperature and slag composition.

Jan 1, 2003

By Shengqi Chen

The reduction smelting of nickel laterites produces slag, consisting principally of the chemical components MgO, "FeO", SiO2, and A12O3, and ferro-nickel alloy. Despite the fact that the phase equilibria for the ternary MgO-"FeO"-SiO2 up to 1500°C is well established limited experimental data are available in the MgO-"FeO"-SiO2-Al2O3 system, which is relevant to commercial operation of the process. A methodology has been developed for the experimental investigation of the liquidus temperatures for the multi-component system MgO-"FeO"-SiO2-Al2O3-Cr2O3 in equilibrium with metallic iron. Experiments have been carried out using high temperature equilibration, quenching, followed by electron probe X-ray microanalysis (EPMA). Liquidus temperatures have been determined in the silica primary phase field in the composition ranges directly relevant to the Cerro Matoso S.A. ferro-nickel smelting slag. Liquidus isotherms have been determined for temperatures between 1450 to 1600°C. The study enables the liquidus to be described for a range of MgO/FeO ratios. It was found that liquidus temperatures in the silica primary phase field decrease significantly with the addition of AI2O3. Keywords: Liquidus temperature, ferro-nickel, pyrometallurgy, smelting

Jan 1, 2004

"Mixing phenomena in a bottom blown air-stirred one-seventh water model of CLU (Creusot-Loire Uddeholm) reactor was studie9-using three different configurations of straight circular nozzles fitted axially at the bottom of the vessel. The mixing time has been determined by pH measurements at various gas flow rates, bath heights and nozzle orientations in the presence and in the absence of a second phase.Experimental results reveal that the mixing time decreases with increasing gas flow rate. For a given gas flow rate the mixing time increases non-linearly with increasing bath height. Off-center configuration gives slightly lower mixing times as compared to center configuration. It is found that the contribution of buoyancy to the total stirring energy density is very small, but its contribution increases with increasing bath height. In the presence of an upper oil layer, the mixing time increases significantly for all configurations.IntroductionIn high temperature metallurgical melts mixing is carried out by injection of a gas either from top or bottom of the vessel in order to accelerate the rates of chemical reactions and to promote bath homogenization. When a gas is injected into a liquid through a submerged lance, porous plug or nozzle, the gas, rising as a two phase plume to the surface, imparts momentum to the surrounding liquid and causes gross circulation in the bath which promotes mixing."

Jan 1, 1997

By W. K. Choi

Stainless steel exposed to wet environments at ambient temperature is subject to the formation of a surface biofilm. Depending upon the prevailing environmental conditions (dissolved oxygen, pH, Eh, concentration of cationic/anionic species), the biofilm may stimulate corrosion through formation of differential aeration zones and concentration cells. Corrosion significantly impacts the United States economy, since on a yearly basis, corrosion induced losses are estimated to be over $200 billion. A large portion of this corrosion is imputable to bacterial activity, and basic information is needed for a better understanding and control of the biocorrosion phenomenon. The present study has investigated the influence of Thiobacillus ferrooxidans in the corrosion of American Iron and Steel Institute (AISI) 304, 316 and 416 stainless steel samples. The formation of biofilm and microstructural changes on the surface of stainless steel samples and their weldments were assessed by microscopic examination, and the changes in the mechanical properties by stress-strain measurements. The significance of the results will be discussed.

Jan 1, 1993

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 P. Lussiez

Precipitates consisting of amorphous ferrihydrite and crystalline goethite have been prepared by aging hydrolyzed Fe (III) solutions at room temperature. The precipitates have been characterized by x-ray diffraction and differential thermal analysis. The amorphous ferrihydrite transforms to goethite with time. The ferrihydrite to goethite transformation is affected by the presence of small amounts of copper or nickel coprecipitated with the iron. .The addition of copper decreases the amount of goethite at a given aging time and increases the amount of coprecipitate which is initially dissolved in sulfuric acid, but it does not seem to affect the dissolution of the crystalline part'. It is proposed that adsorption of copper hydroxo species on goethite nuclei delays the ferrihydrite to goethite transformation. The effect of nickel is less dramatic than that of copper. Apparently a portion of the added nickel is adsorbed on the goethite crystallite surface rather than incorporated into the goethite lattice.

Jan 1, 1981

By R. L. Nyirenda

One of the problems with ammoniacal-ammonium carbonate leaching of EAF carbon steelmaking flue dust is that zinc present in spinel phases is not leached. This paper presents results of test work in which prior to leaching, EAF dust was reduced with CO containing gas to decompose the spinels into zinc oxide and iron bearing phases, mainly metallic iron and wustite. From such reduction products, the amount of zinc leached increases but the iron co-leached becomes extensive. The effect of various leaching parameters such as liquor concentration and redox potential on zinc and iron dissolution has been investigated. Supplementary experiments utilizing pure zinc oxide and pure iron phases were also carried out. Results show that the co-dissolution of iron from severely reduced EAF dust cannot be prevented. This is because the wustite phase contains zinc which can only be leached when iron also dissolves. Further, the zinc bearing wustite phase is not totally soluble so that the residue cannot be made zinc free. In the absence of air, dissolution of metallic iron hardly occurred, though in leaching experiments of a long duration its transformation to a spinel structure was observed.

Jan 1, 1992

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, Pso, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of 02 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By J. Wong

We report a successful use of x-ray absorption spectroscopy to probe the chemical and structural environment of trace elements in coal. When applied to vanadium in coal, it was found that vanadium exists in at least two environments: a trivalent site 6-fold coordinated by oxygens at ca. 2.0~ and a tetravalent site 5-or 6-fold coordinated also by oxygens, one of which forms a short V=O bond at ca. 1.6a. No evidence of nitrogen (porphyrin)1'or sulfide environment was found. It was also found that the vanadium environ-ments in the raw coal did not survive unchanged in a liquefaction process. These findings have implications for coal cleaning processes and for trace element release into liquefaction process streams.

Jan 1, 1982

By Gaballah I.

Elimination of arsenic, mercury and zinc from synthetic solutions containing H;\A.sD4. HgCI2 and ZnCI2 using modified barks was investigated. The pH range was varied from ?1 to 10. The initial concentrations of individual element were 10,100 and 1000 ppm. More than 99 % of mercury and 65 % of zinc cations were removed by the modified bark .. In this case, the modified bark reacts as a cation exchanger leading to the release of ' two protons for every HgII or ZnII fixed by this material. About 30 % of arsenic was eliminated from the solution. This 'low efficiency could be attributed to? the presence of arsenic ,as. anion. Decontamination of a treated industrial effluent containing 4 ppm of ion? metals was performed on a pilot plant scale by the modified bll(k. More than 70'% of these ion metals were eliminated.

Jan 1, 1995

By J. D. Law

The presence of long-lived radionuclides presents a challenge to the management of radioactive wastes. Separation of the radionuclides from the waste solutions has the potential of significantly decreasing the costs associated with the immobilization and disposal of the waste by minimizing waste volumes. Several solvent extraction processes have been developed at the Idaho National Engineering and Environmental Laboratory for the separation of transuranic elements (TRUs), 90 Sr, and/or 137 Cs from acidic radioactive waste solutions. The TRUEX and POR processes for the separation of TRUs, the SREX process for the separation of 90Sr, the cobalt dicarbollide process for the separation of 137Cs and and a universal solvent extraction process for the simultaneous separation of TRUs, 90Sr, and 137Cs have all been developed in centrifugal contactors using actual liquid radioactive waste solutions and simulated dissolved calcine waste solution. In addition, the behavior of metals with each of the solvent extraction processes was evaluated. This article summarizes the most recent results of the each of the flowsheet demonstrations and provides Information on the centrifugal contactor equipment used for the testing.

Jan 1, 1999

Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

By Shengli Wu, Fengjie Zhang, Feng Chang, Hua Lu, Kaiping Du

In order to make a complete understanding of steel plant metallurgical dusts and to realize the goal of zero-waste, a study of their properties was undertaken. For these purposes, samples of two sintering dusts (SD), two blast furnace dusts (BFD), and one electric arc furnace dust (EAFD) taken from the regular production process were subjected to a series of tests. The tests were carried out by using granulometry analysis, chemical analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy via SEM (EDS), and Fourier transform infrared spectroscopy (FTIR). The dominant elements having an advantage of reuse are Fe, K, Cl, Zn, C. The dominant mineralogical phases identified in sintering dust are KCl, Fe2O3, CaCO3, CaMg(CO3)2, NaCl, SiO2. Mineralogical phases exist in blast furnace dust are Fe2O3, Fe3O4, with small amount of KCl and kaolinite coexist. While in electric arc furnace dust, Fe3O4, ZnFe2O4, CaCO3, CaO, Ca(OH)2 are detected.

Jan 1, 2015

By F. Patisson

During exothermic gas-solid reactions, heat generation makes temperature rise and modifies the rate of the various mass transfer processes, namely the chemical reaction itself, the pore diffusion and the external transfer. We have investigated this thermal effect during the oxidation of zinc sulfide porous pellets in a thermo balance furnace, between 550 and 900°C-and under O2-N2 atmosphere. The results have been' analyzed by using, firstly, the law of additive reaction times derived from the isothermal Grainy Pellet Model, and, secondly, a new numerical model taking into account non-isothermal conditions. Both the models can satisfactorily simulate conversion versus time, but the numerical model also depicts the temperature evolution within the pellet. Finally it is shown that owing to the heat generation the zinc sulfide oxidation takes place under diffusion control (3/4 internal, 114 external) in all the cases studied. During the course of reaction, the. pellet undergoes strong temperature variations, with thermal gradients confined to a shell oxide layer.

Jan 1, 1996

By Dean Ilievski

Mathematical modelling of the precipitation process requires that the kinetics of crystal growth, nucleation and agglomeration be known: This paper reviews the current state of knowledge on these precipitation sub-processes (ie. growth, nucleation and agglomeration) and describes a number of experimental techniques for estimating their kinetics. The experimental methods used to generate the precipitation data and the data analysis techniques used to extract the kinetics information from the data are discussed separately. There is no universal "best" technique for determining the kinetics. However, studies on multi-crystal systems are more reliable for modelling purposes than are single crystal studies. The selection of a technique will depend on which sub-processes are present. A problem with all kinetics studies is that there is generally a large uncertainty in the estimated kinetic parameters. This stems from the scatter in the experimental data being further propagated by the mathematical techniques used to extract the kinetic parameters.

Jan 1, 1996

By Qinmeng Wang

The oxygen bottom blown copper smelting process is a new technology which has been widely applied to the copper production in China. In this work, a computational thermodynamics model for this technology has been established, based on smelting mechanism and theory of Gibbs free energy minimization. The calculated results from the model agree well with the actual industrial data, indicating that the model can be used for the predictions under different operating conditions. The tendencies of the key parameters (such as Cu losses and Fe3O4 content in slag) and the distribution ratios of the minor elements (such as Pb, Zn, As, Sb and Bi) can be predicted by adjusting the oxygen/ore ratio charged into the bottom blown copper smelting furnace. The model can be used to monitor and optimize the industrial operations of the oxygen bottom blown copper smelting process.

By Saskia Duyvesteyn

Small ion-exchange resin particles provide faster mass transport than conventional-sized beads. Unfortunately, high pressures are needed to pump solutions through columns containing small resin particles. It is preferable to disperse fine resins in the solution being treated. Screens have been used to separate the resin from the solution, but screens do not retain fines created by attrition of the resin particles. We have developed a separation process based on flotation, which relies on the surface characteristics of the resin, instead of size. The resin is conditioned with a surfactant before dispersing it in the solution to be treated; this increases the hydrophobicity of the resin sufficiently for froth flotation, without introducing surfactant directly into the solution. The surfactant adsorbed on the resin surface does not appear to impair the kinetics of metal ion removal. A flowsheet for an effluent treatment process is proposed; other applications are clearly possible.

Jan 1, 1998

By Randall M. Gennan

Generally sintering is focused on the bonding of particles at high temperatures; possibly with simultaneous densification. However, an important aspect of sintering occurs during heating at relatively low temperatures where polymer processing aids are removed via control of the atmosphere, heating rate, or hold time at intennediate temperatures. New insights into burnout processes show impact from the polymenype, particle size, amount of polymer, atmosphere, part geometry, and thermal profile. This presentation focuses on the key parameters to demonstrate improved mechanical property levels are available in traditional powder metallurgy alloys by proper selection of the processing polymer and proper care in its thermal extraction. The focus is on mechanical property, where gains up to 40% are demonstrated due 10 changes in the processing polymer. Further, atmosphere control during polymer burnout provides a benefit by allowing formation of desirable carbonitrides, giving strength levels over 3 GPa (over 400 kpsi). Insight is? gleaned from powder injection molding, where high polymer contents mandate proper processing control.

Jan 1, 1996