Search Documents

By K. Osseo-Asare

"The molecular structural and solution chemical characteristics that underlie the surface activity of solvent extraction reagents are highlighted, with particular emphasis on the tendency towards reverse micelle and microemulsion formation. The physicochemical factors that lead to microemulsion-enhanced solvent extraction with chelating extractants are elucidated. Membrane-based contactor systems are described which are uniquely suited for enhanced solvent extraction with microemulsions. The possibility of combining solvent extraction with microemulsion-mediated materials synthesis is discussed. IntroductionThe discovery of new selective extractants has resulted in major breakthroughs which have helped to establish solvent extraction as a versatile separation technology (1-3). A complementary strategy towards new process development is to seek new ways of using the available reagents. This paper explores this second approach. From a molecular structural standpoint, an extractant may be viewed in terms of two components: a polar functional group and a hydrocarbon radical. In the conventional view of solvent extraction, this molecular structure serves two main purposes: The polar functional group provides the binding sites for complexation of metal ions, while the organic group is needed to render the resulting metal-extractant complex organic-soluble. But are these the only properties of the organic and the polar groups that are relevant to the solvent extraction process?In this paper, attention is directed to the fact that solvent extraction reagents possess the molecular structures of amphiphiIes; that is, they are characterized by the presence of spatially separated hydrophilic and hydrophobic groups on the same molecule. A case is made for the view that this amphiphilicity offers interesting opportunities to develop new separation processes which collectively may be described as enhanced solvent extraction (4-6)."

Jan 1, 1996

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 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 B. Nowak

For sources with an iron-to-vanadium ratio of far above 1, it is proposed to leach in acid and to oxidize under autoclave conditions. During this oxidation process, it is experimentally shown that divalent iron contained in this solution will be oxidized to trivalent iron, whereas free acid contained will be consumed by this reaction. In case no acid is present or already fully consumed, a solid consisting of ferric compounds and an iron-vanadium-co-precipitate will form that can be filtered from the solution. If choosing the right reaction conditions, this filter cake has an iron-to-vanadium ratio of close to 1, whereas the liquid remainder is almost vanadium free. This precipitate, identified as FeVO4, 1.1 H2O, can be processed by conventional technologies such as caustic leaching, or probably salt roasting or reduction with aluminum, yielding common marketable products.

By S. N. Sinha

The distribution coefficients of lead and silver between copper and matte phases have been measured at two different temperatures. Experiments covered the ranges of 0.009-1.8, 0.07-0.13, and 0-11 wt pct lead, silver, and iron in matte, respectively. The distribution coefficients of lead have been measured at 1405 and 1505 K and correlated with lead and iron concentrations in metallic copper and matte. The values of the distribution coef¬ficient of lead between copper and iron-free matte, at infinite dilution of lead, have been determined to be 3.60 and 4,06 at 1505 and 1405 K, respectively. The distribution coefficient of silver between copper and iron-free matte is independent of silver concentrations and has been measured to be 2.13 and 2.21 at 1400 and 1500 K, respectively. For an iron-bearing matte, the distribution coefficient of silver has been correlated with iron concentration in the matte at both 1400 and 1500 K. From the measured values of distribution coefficients, the Raoultian activity coefficients of PbS and AgS0.5 in copper-saturated matte have been calculated. At infinite dilution, the following equations correlating the Raoultian activity coeffici¬ents of PbS and AgS0.5 with matte- composition and temperature have been obtained: log Y° PbS =1.515 + 1080/T 0.14 NFes lbS Fog YAgS = -0.074 - 425/T + 0.09 NFes. - 0.5

Jan 1, 1983

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 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 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 Zhao Guangwen, Wu Tan, Qiuzhan Tian, Duan Shuzhen

"A thorough study of lost currents in bipolar cells has been made for the development of the great potential of bipolar cells in energy saving. A proper equivalent circuit for bipolar cells has been found, and mathematic methods for computing lost currents at all kinds of polarization have been developed.At linear polarization, the lost currents can be computed by solving either a tridiagonal matrix or an ordinary differential equation of second order. This kind of values can be used to evaluate the minimal lost currents at given conditions. At other kinds of polarization, the lost currents can be computed by the same methods as above if the necessary experiments of measuring the cell voltages of every electrolytic compartment have been made. This kind of values can be used to design bipolar cells at practical conditions.Extensive experiments have been made to evaluate the effects of electrode polarization, emf of galvanic cell for the formation of electrolyzed substance, gaseous products, geometric dimensions of electrolytic cells, special resistance of electrolyte used, and the total and ordinal number of electrolytic compartments on lost currents. It is the first time to make such a systematic research by experiments in the world. Experiments showed that theoretic models were in good agreement with measured data. Experiments also showed that D.C. energy consumption of 0.45 kwh/kg of Pb for lead electrolysis from molten chlorides could be achieved in a cell with 7 bipolar electrodes.IntroductionIt is very promising to apply bipolar electrolytic cells to electrolysis of aluminum, magnesium, lead, zinc and perchlorinates for their great potential of energy saving for example, bipolar cells had been used in the production of magnesium and saved more than 30% of energy, being one of the three main techniques of energy saving in the production of titanium sponge (1)."

Jan 1, 1988

By I. Gaballah

The chalcopyrite ore's anodic and cathodic electrodissolution are studied using a Porous Pulsed Percolated Electrode (3PE) reactor. Stationary solid electrode experiments are also performed to explore the mechanism of electrochemical dissolution of chalcopyrite. Experiments with a low - grade natural ore have been carried out at 25 "C in solutions containing 1 M NaCl and 1 M HCl. Galvanostatic and potentiostatic conditions are employed. The influences of current and potential on selectivity of the chalcopyrite ore dissolution are assessed. Anodic oxidation of this ore leads to a preferential dissolution of iron bearing minerals, whereas cathodic reduction is more selective with respect to chalcopyrite. However, in both cases the electrochemical dissolution is incomplete and the current efficiency is low. Design of the actual reactor has to be modified to increase the bed conductivity and to allow continuous experimentations.

Jan 1, 1994

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 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 K. C. Liddell

"Cu/Ni multilayers exhibiting giant magnetoresistance were deposited from a single electrolyte under stepped potentiostatic control. To enable transport measurements to be made without remounting the multilayer film, we developed a novel method that involved plating on a thin metallic basal layer atop a rigid non-conducting Si substrate. Rotating ring-disk electrode techniques were used to monitor the composition and thickness of individual plated layers. Transmission electron microscopy confirmed that the interfaces between adjacent layers were sharp and that the structure of the layers was uniform throughout the film. Atomic force microscopy images indicated that the film's surface was smooth and free of defects.ELECTRODEPOSITION OF THIN MULTILAYER MAGNETIC MATERIALSI. IntroductionElectrodeposition of compositionally modulated films will in all likelihood continue to be used to produce the read heads for stored magnetic data. However, the next generation of head materials will require both improved sensitivity and reduced film thickness. Certain multi layers consisting of thin alternating ferromagnetic and nonmagnetic layers exhibit giant magneto resistance and consequently are promising candidates for read head applications. We have successfully made multilayer films with giant magnetoresistance that have total thicknesses as low as 25 nm, approximately 120 times thinner than the thinnest similar films reported in the literature. This paper describes early results from our work on electrodeposition and characterization of Cu/Ni multilayers, a model system with enhanced magnetic and mechanical properties, including the GMR effect. The structure and composition of the multilayers were determined using TEM, AFM, and electrochemical methods, and their magnetoresistance was measured by the standard four-probe technique. A novel method developed in this work enabled the transport properties of the ultrathin films to be measured reliably without the need to dissolve the cathode or handle the films. To provide a context for these results, short accounts of other work on giant magnetoresistance and multilayer electrodeposition are also included."

Jan 1, 1997

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 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

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 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

By R. L. Nyirenda

An investigation of the reducibility of a cassiterite concentrate with charcoal was made in the temperature range of 1123-1373 K. The course of the reaction was monitored by a combination of sample weight loss measurements, product gas analysis, and chemical analysis of the reaction product. It was found that the cassiterite could be best reduced by a combination? of high temperature, reasonably high charcoal proportions, high charge poroslty, and the addition of a small percentage of lime. Analysis of kinetic data obtained from isothermal experiments using theory from the oxidation of carbon by carbon dioxide gave an activation energy value of 255 lci/mole for the consumption of carbon by reaction with cassiterite.

Jan 1, 1990