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By Timothy W. Ellis

"This paper presents the basic theory of operation, physical chemistry and phase equilibria which allow the development of liquid-liquid extraction circuits based on metallic solvents. The incorporation of reduction and reduction/diffusion processes into the process scheme is discussed and a detailed description of several liquid-liquid extraction schemes are developed. A synopsis of experimental results obtained using this method to separate rare earth and other metal based materials will be given.IntroductionConcerns over the effects of waste materials in the environment has been one of the significant social hallmarks of the late 20th century. Essentially every industrialized country has had to incorporate the cost of waste material into the equation of production. Legislative initiatives have led to the passing of very tough laws, by historical standards, which govern the environmental impact of materials processing.Liquid-Liquid extraction is a very common unit operation normally using aqueous and/or organic based solvents. Early work at the Ames Laboratory focused on the use of this technique for the reprocessing of spent fuel from liquid metal breeder reactors by the use of metallic solvents. Recently, we have revisited this area as a means to recycle/reprocess several emerging rare earth based materials, although this method has a much wider range of application. The reinvestigation of this technology is particularly timely as hydrometallurgical based processes are coming under increasing scrutiny in the U.S.A. by the Environmental Protection Agency (EPA). Although technology currently exists to remove contaminants from aqueous based waste streams, often the application of such methods is expensive. With proper design and judicious selection of reagents liquid metal extraction can achieve a high recovery along with a benign waste stream.This process has several possible advantages over other technologies. First is the elimination of aqueous solvents. Therefore, problems associated with disposal or reprocessing of the aqueous carrier are eliminated. Second, with proper system design, very high separation coefficients can be obtained thus limiting the number of stages required. Third, metals are extracted from metals with a metallic product, thereby eliminating the need to re-reduce metal for oxides or other compounds which are the common output for aqueous based extraction procedures."

Jan 1, 1996

By G. G. Richards

The zinc slag fuming process is used to recover zinc from molten iron-calcium silicate slags by treatment with pulverized coal and air. The rate of zinc fuming is controlled by the complex interaction of several kinetic factors including the rate of entrainment of coal in the slag, the extent of the coal-slag reaction and the rate of ferrous oxide oxidation to ferric oxide. This paper briefly outlines the mechanism of fuming and, on this basis, optimization of process parameters is discussed. Modelling analysis and recent industrial trials at Cominco show that coal entrainment in the slag, bath temperature, and bath depth are critical variables affecting process rate and efficiency. The first step in process optimization is to assess coal bypass of the bath. In general, changes which promote operation at a higher temperature, greater coal entrainment in the slag and extended residence time of the coal in the bath increase fuming performance. Coal entrainment is controlled by injection conditions whereas bath temperature is a function of coal combustion and ferrous oxide oxidation. Residence time of the coal is largely a function of bath depth. The implication of model predictions for continuous fuming is shown.

Jan 1, 1994

By Adam Powell

A Cahn-Hilliard phase field model is formulated to describe transport-limited electrochemical reactions coupled with fluid flow in a metal reduction cell. When the reaction is limited by mass transfer of metal ions from the electrolyte to the cathode, the metal-electrolyte interface at the cathode exhibits a Mullins-Sekerka instability, leading to the growth of dendrite-like "streamers" of liquid metal into the electrolyte, which in turn significantly enhance the apparent mass transfer coefficient there. Model results for iron reduction from ferrous oxide in slag show formation of these streamers. Although the double-layer is not included in this model, the related phenomenon of electrocapillarity can be represented by a gradient penalty term which includes the electric potential gradient, such that interfacial energy is a function of the electric field normal to the interface.

Jan 1, 2003

By Natasa Mitevska

The statistical analysis of the slag composition influence on copper losses to discard slag in the reverberatory furnaces No.1 and No.2 in the RTB BOR, Copper Smelter and Refinery (Yugoslavia) is presented in this paper. The model for the slag basicity calculation is determined, and connected to the copper distribution coefficients between the matte and slag phase. The influence of all components on the slag structure is also illustrated.

Jan 1, 2003

By Xiaodi Huang, Matthew Andriese, Zheng Zhang, Jiann-Yang Hwang, Zhiwei Peng

"The thermal decomposition and regeneration behaviors of wüstite were investigated by in situ high temperature X-ray diffraction (HT-XRD) under non-isothermal condition at heating rate of 4 K min-1 in vacuum ranging from 294 K to 973 K. Wüstite on heating decomposes to magnetite and iron up to 823 K, above which it exhibits marked tendency to regenerate. Investigation of thermal stability of the reaction system shows that the decomposition proceeds under kinetic reaction control while the regeneration is under thermodynamic control. Kinetics study based on the Coats-Redfern integral approximation method indicates that the decomposition reaction follows a Komatsu-Uemura model-based diffusion-controlled kinetics with activation energy of 32.860 kJ mol-1. The thermodynamics analysis of regeneration reaction demonstrates that wüstite regenerates at lower temperature than stoichiometric ferrous oxide.IntroductionOwing to its importance in preparing various magnetic ceramic/metal nanocompostites or nanocrystals with high values of coercivity for the application as recording media, wüstite (non-stoichiometric ferrous oxide) has been attracting the attention of scientists over a long period [1-6]. The thermal behavior of wüstite was investigated by several researchers and phase transformations due to thermal decomposition and regeneration of wüstite during the heating in a specific temperature range was observed [7-9]. In spite of wüstite being found to dissociate to magnetite and iron at temperatures lower than 848 K and then regenerates at higher temperature, a clear understanding of the reaction mechanisms is clearly lacking [9]."

Jan 1, 2012

By G. G. Krishna Murthy

Several experiments were conducted to determine the rates of heat transfer coefficients of CaO-SiO2-A1203-FeO slags at temperatures in the range 1623-1823 K The experimental technique involved measuring heating rates of a solid specimen, sub¬merged in slag phase, using a temperature probe made of Pt\ 10%Rh-Pt. Effect of %FeO (3-10%), %FeS (0.1-0.68%), %P205 (0.2-3.0%), %MgO(5-6%), and %MnO (0.96-3.84%) present in the slag on overall heat transfer coefficient, U, of slags was investigated. Simple first order heat balance equation in combination with experimental plots rising temperature of solid specimen versus time were employed to determine the values of U. The values of U determined in the present investigation were present in the range of 70-260 cal/Ks.m2. The value of U increased with increasing the slag temperature. The values of U were not effected by increased amounts of sulfur in the slag phase. The increased concentrations of MgO, FeO, MnO, and P205 in the slag phase decreased the values of U. On the other hand, the increased amounts of Fe2O3 in the slag phase increased the value of U. Comparison of the results, obtained using the slag bath stirred by argon injection, with those determined without any stirring indicated that both radiative and conductive heat transfer mechanisms are important even at high temperatures.

Jan 1, 1993

By Michael S. Moats, Daniel Kim, Shijie Wang

"The behavior and deportment of lead, arsenic, antimony and bismuth are critical in producing high quality cathode by copper electrorefining. A critical review of research related to these elements is presented along with a comparison to industrial data, where appropriate. These elements exist predominantly in the anode as complex oxides along die grain boundaries. Upon dissolution, Group 15 elements report both to the electrolyte and slimes while lead essentially enters the slimes. The deportment of the Group 15 elements appears to be influenced by several chemical interactions which are discussed. The effect of these elements on floating slimes and anode passivation is reviewed. Under normal electrorefining conditions, lead, antimony and bismuth are thought to enter the cathode through the encapsulation of slime particles. The literature indicates that arsenic enters the cathode predominately by electrolyte entrainment. Finally, areas for future research regarding these elements are presented.IntroductionControlling lead, arsenic, antimony and bismuth is critically important for the production of high quality cathode in copper electrorefining. The reasons for this are twofold. First, ASTM Grade 1 Cathode specifications [1] for these elements are low, as listed in Table 1. Second, they can affect the efficiency of the electrorefining process (e.g., through passivation, current efficiency, slime processing)."

Jan 1, 2012

By Ernt. W. D.

A membrane based mixed extractant process was developed for selective removal of copper from waste acidic cupric chloride etchant solutions found in printed wire board manufacturing. The process uses a mixture of Adogen 381 (tri-isooctylamine), MOC®-45 (ketoxime) and MOC® 55TD (aldoxime) in a kerosene diluent. The mixed extractants recover the copper from a hydrochloric acid medium and transfers it to a sulfuric acid medium. The process also utilizes unique wetted membranes to separate the aqueous and organic phases. The driving force for these membranes is not pressure but the difference in surface tension between the two phases. By using these membranes, complete phase separation results. There is no physical entrainment contamination as found in conventional systems. The only cross contamination is the solubility concentration of one phase in the other. This however is less than 10 mg/l.

Jan 1, 1998

By F. Shahbazian

attempt to systematize the knowledge on slag viscosities, the present work was carried out. The Among the physical properties of slags, viscosity is very important in understanding the mass out in the temperature range 1438-1762 Q The rotating cylinder method was used in the viscosity measurements. Crucibles and spindles made out of pure iron were employed. The transfer phenomena in metallurgical processes. The viscosities of fayalitic slags are of great interest in the non-ferrous metal industry, with special reference to copper production. In an slags were prefused before the measurements. In order to take into account the vaporization reactions involving CaF2, pre- and post measurement samples of the slags were chemically analysed and the compositions were ascertained. The results show that in the case of the CaO-SiO2 system, CaF2 additions tend to decrease the viscosity, in accordance with the expectations. In the case of the "FeO"-SiO2 system, at higher "FeO" / SiO2 ratios in the slags, a reverse trend was observed. The results are discussed on the basis of a viscosity model for silicate melts developed in the present laboratory as well as the structural considerations of silicates.

Jan 1, 2000

By Norimasa Yamasaki, Masao Kurosaki

"The effects of plating conditions on the crystal orientation of electrodeposited zinc were investigated by varying elecyrolyte flow rate and current density. Precipitation of the Zn (00 • 2) basal plane is promoted at lower current density and higher flow velocity. Effect of the flow velocity on the mass transport was evaluated based on the polarization measurement in which Cu was used as the tracer. As a result, it has been clarified that the crystal orientation of electrodeposited zinc can be uniquely arranged by the overvoltage (iU0.5) that can be simply calculated by considering -the current density and boundary layer thickness. At the same time, the electrode potential during electrodeposition that can be calculated by using a model based on the competitive reactions of hydrogen reduction 'and zinc reduction exhibits an extremely good correlation with the crystal orientation of electrodeposited zinc.Introduction Electrogalvanized steel sheet has better surface properties than hot-dip galvanized steel sheet, and is used in home electric appliance and automobile applications. Factors such as crystal morphology, crystal orientation and surface roughness have a large influence on its appliance, formability and corrosion resistance [1-3].Electrolysis, condition, bath composition and alloying elements are reported as factors that affect the crystal orientation of the electrogalvanized coating. Factors that can be controlled on time in the production site are electrolysis condition that-is current density and plating solution flow velocity.Some studies[4-6] report that the crystal- orientation of the Zn(00 • 2) plane is increased by promoting, the mass transfer of zinc ions in the plating solution or decreasing the concentration overvoltage, but did not investigate in detail the plating solution flow conditions in the plating cell nor quantitatively determine the effects of both current density and plating solution flow conditions on the crystal orientation of ' electrodeposited zinc."

Jan 1, 2000

By C. Beckermann

"A diffuse interface model is derived for the direct simulation of two-phase flows with surface tension, density differences between the phases, and phase change. The derivation starts from the balance equations for a sharp interface and uses a formal averaging procedure on an atomic scale to obtain diffuse interface versions of the equations. Two approaches are considered: (i) the two phases have different velocities inside the interface and separate conservation equations are solved for each phase, and (ii) the two phases have the same velocity inside the diffuse interfuce and mixture conservation equations are solved. Based on a superposition of microscopic (atomic-scale) and macroscopic interface morphologies, an expression for the interfacial momentum source term is introduced that models surface tension effects and accounts for immiscibility between the phases.IntroductionDiffuse interface methods have been a popular tool in the direct simulation of two-phase flows [I]. In diffuse interface approaches, the interface between the two phases is characterized by a rapid but smooth transition in the properties, such as density and viscosity. Usually, a phase function ? is introduced to represent this transition, and the evolution of ? in the domain is computed from a separate equation or recipe. A unique set of conservation equations (e.g., mass and momentum) is solved on the entire domain, irrespective of the phase present, by accounting for the transition in the properties and introducing terms that account for interfacial sources. The continuum surface force (CSF) model of Brackbill et al. [2], which accounts for surface tension, is an example of the latter. The volume-of-fluid (VOF), level set, and phase-field methods are all examples of diffuse interface approaches. The major advantage of diffuse interface methods is that explicit tracking of the interface and the application of traditional sharp interface conditions are avoided. A disadvantage can arise from the artificial smearing of what is in reality an interface of atomic-scale width; however, techniques have been developed to overcome this problem."

Jan 1, 2004

By Kenneth P. Michalek, James E. Kelly, Jonathan A. Dantzig

"Many investigations have been reported regarding the simulation of continuous casting with emphasis on in-mold heat transfer. These analyses have been limited, however, because they require either estimation or measurement of the characteristic heat transfer between the ingot and the mold. In this paper, a self-consistent model 'is presented for calculating the heat transfer between a solidifying continuous casting and the mold, in the context of the continuous casting of steel. Using both thermal and stress analyses, the air gap formed during continuous casting is calculated and used to compute the heat transfer coefficients. Iteration between the thermal and stress analyses is used to determine a self-consistent solution. IntroductionThe continuous casting process for steel is illustrated schematically in Fig. 1. Molten steel is tapped into a tundish from which it flows at a controlled rate into the continuous casting mold. The initial shell of the casting forms in the mold by transfer of heat from the metal through the mold wall to the cooling water. The remainder of the casting is solidified by application of water sprays, and/or radiation cooling below the mold.Heat transfer in the mold portion of the process is important because it controls the formation of various defects which are deleterious to subsequent processing. Examples of defects formed in this region are surface irregularities, such as cold folding and oscillation marks, and more serious defects, such as longitudinal or transverse cracks. A more catastrophic problem which may occur is a breakout, in which the shell ruptures and molten steel is discharged in an uncontrolled way."

Jan 1, 1986

By N. Krishna

The utilization of Electrochemical Impedance Spectroscopy (EIS) in conjunction with Atomic Force Microscopy (AFM) is a powerful surface characterization technique to study the role of sulfur formation during acidic oxidation of chalcopyrite. It has been established that the chalcopyrite dissolution kinetics is controlled by the formation of passive sulfur layer during leaching. The objective of the study was to characterize the intermediate sulfur layer formation at different oxidation conditions in acidic solution. The chalcopyrite samples were subjected to anodic oxidation and the oxidation process was analyzed using impedance spectroscopy. The sulfur growth on the chalcopyrite surface during oxidation was further analyzed using Atomic Force Microscope for sulfur roughness and grain size, peak height and sulfur growth.

Jan 1, 1999

By D. J. Webb, D. G. Reynolds, D. W. Ashman, D. W. Goosen

Cominco Limited operates an integrated zinc-lead complex at Trail, British Columbia, Canada. Central to the successful operation of this complex is the treatment of zinc leach residues through the lead smelter. In 1997, Cominco started up a new lead smelter using KTVCET flash smelting, a state-of-the-art conventional slag fuming furnace, and a new drossing plant. The smelter has fully met the requirements for environmental performance, reduced energy consumption, and lowered labour costs. This paper provides a description of the new smelter and discusses the problems encountered during the start-up, as well as the solutions to those problems. Recent operating results are presented. Lead-Zinc

Jan 1, 2000

By Roberto Parreiras Tavares, Frederico da Costa Fernandes, Guilherme Antonio Defendi, Vangleik Ferreira da Cruz, Júlio César de Sousa Pena

"Near-net-shape casting is an important area of research in the iron and steel industry today. Among the near-net-shape casting processes, the single-belt caster seems to be the most promising, since it is the only one that can achieve levels of productivity similar to those obtained with conventional continuous casting machines. One of the most important aspects in the single-belt casting is the feeding system used to deliver liquid metal over the belt. This system determines the velocity distribution and the levels of turbulence of the liquid metal and affects the quality of the strips. In the present work, a metal delivery system having a simple geometry was proposed. Using the CFD code CFX 5.6, a mathematical model to simulate three-dimensional turbulent fluid flow and heat transfer in that system has been developed. This model was used to analyze different configurations of the metal delivery system and the free surface shape of the fluid was also determined. A physical model of the feeding system was built and used to validate the predictions of the mathematical model. The fluid flow calculations have been validated by dye injection experiments and laser doppler anemometry. Measurements of the free surface levels have also been performed. These experiments provided supporting evidence for the predictions of the mathematical model.IntroductionTo maintain its competitiveness in the present market, the metallurgical sector, particularly the steelmaking companies, are developing new techniques of production. Some of these new processes are focussed on the strip casting technologies. Among these technologies, the SingleBelt process is considered the most interesting option, reducing the number of rolling steps and, consequently, the final cost of the product, especially the part associated to the energy consumption (fuel and/or electric energy). This process can also reach levels of productivity that can not be matched by other strip casting methods(1). One of the most important aspects concerning these new processes is related to the liquid metal delivery system. This system can have a significant effect on the final quality of the strips, since it determines the velocity distribution and the levels of turbulence of the liquid metal."

Jan 1, 2004

By J. A. Holmes

Due to varying and complex mineralogy, the flotation tailings from the Chingola Concentrator have, for some years, contained upwards of 0.4% acid soluble copper. In 1968, an investigation was initiated, to determine a method for recovering this acid soluble copper. This initial investigation concluded with a recommendation to install a leach-solvent extraction-electrowinning plant at Chingola, to treat up to 900 000 tonnes of material per month, for an additional copper production of some 4 500 tonnes per month. The process consists basically of six stages :- Materials reclamation handling and preparation, acid leaching in air agitated pachucas, solid-liquid separation by countercurrent washing in thickeners, solution concentration and purification by solvent extraction, copper recovery by electrowinning, and residue neutralisation and disposal. This paper describes the development of the main parameters for design of each of the six sections, and gives details of the final plant design. Problems encountered in commissioning and initial operations are commented on, particularly insofar as they indicated any errors or misjudgements in the design. The choice of materials of construction is commented on in some detail.

Jan 1, 1976

By R. Luo, R. V. Kumar

"The co-deposition of cobalt and nickel as a binary alloy has been studied by both cyclic voltammetry and long-period controlled-potential electrolysis. Cyclic voltammetry experiments showed that the cathodic current density for the mixed Co-Ni (Co-Ni=1:3) electrolyte is noticeably higher than that obtained on electrolyte containing single CO2+ or Ni2+ (II) salt of the same ionic strength. The onset potential observed for the mixed salts electrolyte was also less cathodic (negative) than that for the single metal salts, respectively. The effects of a number of operational and compositional parameters on the co-deposition of cobalt and nickel were studied. The parameters under investigation include cathode (deposition) potential, temperature, CI-/Sol ratio in the electrolyte, the amount of additives such as H3B03, and acidity of the electrolyte.Optimum operational conditions were established for the deposition of cobalt and nickel binary alloy. These results are discussed with respect to feasibility of reclaiming cobalt, nickel and chromium from mixed superalloy scraps by melt-refining (under nitrogen and/or ammonia), followed by electrorerining of cast anode for co-depositing Co/Ni and thermal decomposition of chromium nitride for recovering chromium metal."

Jan 1, 1997

By Fuqiang Zheng, Shuai Wang, Ting Duan, Yufeng Guo, Tao Jiang, Andrew Yakovlevich Travyanov

Organic compound binder can effectively enhance the strength of green pellet and reduce the addition amount of binder during pelletizing. However, compared with traditional bentonite binder pellet, the compressive strength of the preheated and roasted pellets significantly declined. It is of significance to resolve this problem for the application of organic compound binder. In this paper, magnetite concentrate was used as raw material, carboxymethyl cellulose (CMC)- bentonite compound was used as binder, characteristics of preheated and roasted pellets and the effects of additives on that were systematically studied, The results show that sodium acetate can effectively improve the characteristics of the finished compound binder pellets. The compressive strength of the preheated and roasted pellets were increased by 52/N·p-1 and 342/N·p-1 respectively when the addition amount of sodium acetate is 2.2%wt of compound binder. Moreover, sodium acetate has no adverse effect on pelletizing process and drying characteristics of green balls.

Jan 1, 2015

By Andrzej Warczok

Liquid slags produced in smelting of copper concentrates contain copper in a dissolved form as well as mechanically entrained inclusions of copper matte. Coalescence and sedimentation of inclusions during slag cleaning plays a key role in copper recovery. Liquid matte inclusion in a molten slag presents a system of metallic conductor in an ionic solution. Constant electric field induces migration of the matte droplet along the current lines. Additional phenomena occur in a system under crossed electric and magnetic fields. Electromagnetic buoyancy force acting on the inclusion affects its settling rate. Electromagnetic buoyancy force of insulating and metal spheres has been measured in a liquid synthetic slag. It was found that depolarisation of the metal sphere, related to the electrode reactions occurring in the surface, plays an important role in the determination of the direction and magnitude of the electromagnetic force. On the basis of the existing theories and results of measurements a mathematical model describing the behaviour of metallic inclusions in the liquid slag under the influence of crossed electric and magnetic fields was developed. Simulation of behaviour of copper matte inclusions under crossed fields showed trajectory of motion in a liquid slag as a function of the slag properties and the inclusion size.

Jan 1, 2003

By Taegong Ryu

The thermal plasma process has been applied to the preparation of nanosized tungsten carbide (WC1-x). The reduction and carburization of the vaporized chloride by methane-hydrogen mixtures produced nanosized WC1-x powder, with a small amount of WC or W2C phase. The products were characterized using XRD, carbon analyzer, and TEM. The effects of plasma torch power, the flow rate of primary plasma gas (Ar) to generate plasma flame, and the addition of secondary plasma gas (H2) on the product composition were investigated. The tungsten carbide (WC1-x) powder had a particle size less than 30 nm. The powder was treated under hydrogen atmosphere to fully carburize the WC1-x, and W2C phases to WC as well as remove excess carbon in the product. Finally, WC powder with a grain size less than 40 nm was obtained.

Jan 1, 2008