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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

Thermodynamics and kinetics? of the removal of Va elements (As,Sb,Bi) from copper were investigated 1n the fire relining by alkaline carbonate fluxes such as Li 2co3 , Na 2CO3 and K2CO3. The distribution coefficients of As, Sb and Bl between alkaline carbonate fluxes and mo) ten copper were ?obtained at 1200°C under the different oxygen potentials. As and Sb were easily removed from copper to fluxes as pentavalent oxide form. On the other hand, Bi was hardly removed except by a Ll2CO3 flux. The removal rates of Va elements from copper were also measured In the temperature range of 1150°C.- 1250°C. The removal rates of As and Sb were much higher than that of Bi. The removal rates of Va elements showed the same order of the distribution coefficients. The removal rate could be expressed by following equation. (1).

Jan 1, 1987

By Nagahiro Saito, Takahiro Ishizaki, Daisuke Yata, Akio Fuwa

"Ternary compound-semiconductor, CuInTe2, film was deposited cathodically under potentiostatic conditions on titanium substrate from aqueous solution containing CuCl2, InCl3, TeO and HCI in this study.The deposition parameters such as electrolytic solution composition, potential and temperature were optimized· for electrodeposition of CulnTe2. Structural characterization of the: deposited film was also carried out using XRD and SEM. Electrodeposited films Were prepared and analyzed for their chemical composition using ICP. The ICP analyses showed that the stoichiometry of the films could be controlled by (1) the deposition potential and/or by (2) the electrolytic bath composition.1. IntroductionThe ternary chalcopyrite type compound semiconductors exhibit such electrical, chemical and optical properties that make them promising for photovoltaic devices (Kazmerski and Wagner 1985)(1). Many researches have been devoted to the characterization of these materials for over one and a half decades. High efficiency solar cells based on p-CulnSe2/n-CdS have been reported (Mickelson and Chen 1983)(2).The electrodeposited fil ns of semiconductors have more advantage than other physical and chemical deposition techniques; it is relatively easy and economic technique and the semiconducting properties such as band-gap variation, concentration of dopant stoichiometric composition and so on can be controlled with some accuracy. The electrodepositions of the ternary CuInS2, CulnSe2 have been reported by many workers (Hodes and Cahen 1986, Bhattachaya 1983, Singh et al 1986, Lokhande and can be prepared as both p-type and n-type. Therefore, its potential for application in optical and photovoltaic devices is one of the great interests. Bhattacharaya and Rajeshwar (1986)(9) reported the electrodeposition of CuInTe2 from an acidic bath· on indium tin oxide (ITO) and Mo substrate. Triethanolamine (TEA) was used as a complexing agent for indium. The electrodeposited CuInTe2 films were non-stoichiometric in composition under all their experimental conditions by electron-probe micro analysis (EPMA) and Auger depth profile analysis. In this paper, we report our results on the behavior .of Cu-In-Te electrodeposition from ·acidic baths; the preparation of CulnTe2 and the effect of bath composition on electrodeposited films obtained."

Jan 1, 2000

By Norihiko Fukatsu, Takashi Iwamoto, Noriaki Kurita, Koji Katahira, Kunihiro Koide, Teruo Ohashi

"The galvanic cell-type hydrogen sensor employing CaZro.9Ino.t03-a. as the solid electrolyte was designed for the measurement of hydrogen activities in molten copper under industrial .conditions. The sensor probe consists of the cap-shaped solid electrolyte with porous platinum electrode on the inside and alumina refractory tube. The gas mixture of the composition 4%H2-0.5%02-Ar was made to flow on the inside electrode. The hydrogen sensor probe was inserted directly into molten copper and the melt was used as the outer electrode. The effect of oxygen activity gradient to EMF was eliminated theoretically by measuring the oxygen activity in the melt simultaneously with an oxygen sensor. The high stability of output and excellent response to the change of hydrogen activity were obtained over the wide range of industrial copper melting conditions.IntroductionIn the metal casting process, hydrogen easily dissolves in molten metals from water vapor in the surrounding atmosphere. Owing to the large difference in hydrogen solubility between liquid and solid metal, dissolved hydrogen becomes a cause of the defects of blowholes in castings or ingots. It is necessary to control the hydrogen content in the molten metals [l]. Using proton-conducting ceramics as a solid electrolyte, high temperature-type hydrogen sensor can be constructed [2]. SrCe03- and BaCe03-based perovskite-type oxides exhibit appreciable proton conduction under hydrogen containing atmosphere at high temperature [3-5]. A hydrogen sensor for molten aluminum using CaZro.91no.103-a. has been developed and widely used in the ·process control in the aluminum melting industry [6,7]. The same type of hydrogen sensor has also been expected in the copper melting industry. .. However, CaZro.91no.103-a shows ·not only proton but also oxide ion conduction in the high temperature and at low oxygen activies like the copper melting· conditions. Then we studied the oxide ion conduction in CaZro.91no.103-a. iit · detail [8]. From the consideration on the EMF of the galvanic cell employing this material as electrolyte, it was shown that the unknown hydrogen activity may be precisely determined from cell potential which is corrected for the effect of oxygen potential gradient And the hydrogen sensor based in this principle was constructed and tested in laboratory-scale [9,10]. We repeated the similar tests in factory-scale and developed the sensor system for practical uses [11, 12]. In this report, the structure and system of the hydrogen sensor for molten copper will be introduced first. The reliability of the sensor will then be demonstrated from the results of experiments for sensor probes carried out in TYK's laboratory."

Jan 1, 2000

By Murali Thirukkonda, Rahul Shah, Srinivas Tangrila, Shankar Rachakonda, Jan Kajuch, Arthur Gurson

"High-temperature superconductors have potential for a variety of applications such as power generators, superconducting magnets for mine sweepers or ship propulsion motors, and magnetic levitation transportation systems. Interest in the use of superconducting wires and tapes increased dramatically after the discovery of high-critical-temperature (high-Tc) oxide superconducting compounds, which offer operating temperatures above that of liquid nitrogen. Several techniques have been proposed to produce commercially viable high-Tc oxide based superconducting wires. One of the promising methods involves multi-pass powder-in-tube (PIT) wire drawing followed by rolling and heat treatment. This work focuses on the development of a numerical model to simulate the PIT drawing process for fabrication of long lengths of silver sheathed Bi-2212 superconducting wires. The finite element based model was used to predict densification of the oxide powder, wire drawing forces, and silver sheath thickness during drawing. A cap-type pressure dependent constitutive equation was implemented in the model to simulate the powder behavior. The model incorporated experimentally obtained material data for the silver and powder. Results indicate that powder densification is increased by decreasing the initial silver thickness and increasing the silver strength. Data from wire drawing experiments were used to verify model predictions. IntroductionSuperconducting wires and tapes can be used to carry large dc currents with no measurable loss due to resistivity. When used in superconducting magnets for power generators, motors, levitation devices, magnetic detectors, or energy storage devices, they could potentially result in significantly reduced energy losses. In the past, most prototypes were tested in liquid helium at 4.2K [1]. However, the necessity to provide liquid-helium cooling systems proved to be a serious limitation in commercialization. In 1986 high-critical-temperature (high-Tc) oxide superconductors were discovered [2], which could allow for higher operating temperatures above liquid nitrogen (77 K). Since then, both academia and industry have concentrated their efforts on the development of high-Tc oxide superconducting wires, tapes and coils. As yet, large scale fabrication of long lengths of these wires with the required current carrying capacity and mechanical properties remains an enormous challenge."

Jan 1, 1994

By D. Doungdeethaveeratana

The extraction kinetics in a novel solvent extraction process have been investigated. In this process, the liquid-liquid emulsion is generated by bottom gas injection into countercurrently flowing aqueous and organic phases. This process has a number of advantages over the mixer-settler unit or the spray column in terms of simple equipment configuration, without any mechanical moving parts, and the ease of cleaning and process control, while providing a sufficiently large interfacial area for rapid mass transfer. The overall rate increased with increasing gas injection rate and height of the aqueous phase but decreased with increasing injector diameter at the same gas injection rate. The variation of the overall rate constant was correlated against a set of dimensionless numbers, representing the operating conditions. Extraction rates and efficiencies comparable to those in a mechanically generated emulsion were attained in this new process.

Jan 1, 1998

By V. Gornitz

The Orphan mine uranium deposit, Grand Canyon, Arizona, is a cylindrical collapse-breccia pipe, 70 to 150 m in diameter and 500 m deep. Pipe fill was derived from the Supai Group, Hermit Shale, and the Coconino Sandstone. Uraninite, with Cu, Fe, Pb, Zn and Ni-Co sulfides is concentrated along the pipe boundary ring fracture (annular ring) and within the central porous sandstone matrix. There is some suggestion of vertical and lateral zonation of U with respect to Cu. Reduction of ferric oxide cement from red beds and recrystallization of carbonate, with formation of kaolinite preceded major ore deposition. Early Ni sulfides, arsenides and disseminated pyrite were followed by massive pyrite, and botryoidal uraninite, which in turn was suc-ceeded by Cu, Zn and Pb sulfides. A second, later generation of uraninite was closely intergrown with hematite and base metal sulfides. Oxidation of primary minerals may have been associated with Tertiary regional uplift. The paragenetic sequence closely resembles that of other Grand Canyon breccia pipes, except for the extensive development of the distinctive uraninite-hematite association. Mineral assemblages at the Orphan suggest possible mixing of the metal-bearing solution(s) with a more oxidized fluid, containing soluble uranyl complexes. Homogenization temperatures of fluid inclusions in calcite (GO-lIO?C) at the Orphan fall within the lower end of the range observed at other breccia pipes.

Jan 1, 1987

By J. Pesl, U. Kemey, F. Sauert

"The CONTOP® smelting cyclone is a water-cooled, upright, high-intensity smelting reactor. The technology for the reactor was initially developed and brought into industrial-scale operation in the area of non-ferrous metallurgy. The two largest smelting cyclones were built with a capacity of 32 tons per hour of copper concentrate mix.The newest industrial CONTOP® plant treats up to five tons per hour of zinc-bearing residues including EAF dust. The highly concentrated zinc-lead oxide produced is sold to the zinc industry. The slag fulfills the leaching criteria and is used in waterway construction. The heat transferred to the cyclone cooling system and the off-gas boiler produces steam from which power is generated in a turbine.V AI has erected a new CONTOP® demonstration plant at MEFOS, Lulea, Sweden. A zinc volatilization rate of 90% was achieved during hot commissioning with Swedish EAF dust.Treatment costs in the range of 85 to 100 EUR per ton were estimated in a feasibility study on the treatment of 73,000 and 57 ,000 tons EAF dust for a group of steelmaking mills in Southern Europe."

Jan 1, 2000

By P. Blazy

A hydrometallurgical procedure for the recovery of metal from ore, particularly of copper from sulphide materials is described. In the course of this procedure, the raw material is first of all submitted to the action of an appropriate reducing system and then treated with a ferric salt solution which brings about the selective solubilisation of the elements to be recovered with respect to those constituting the pyritic phase. This procedure is investigated using two ore samples proceeding from massive sulphide deposits, presenting different chemical and mine- ralogical characteristics. The results of this investigation are compared with those obtained by a classical process employing a ferric salt solution. It appears that one solubilisation of copper takes place under particularly advantageous conditions when our procedure is used. The principal parameters affecting leaching of zinc, lead and copper are examined. The selectivity of this treatment is evaluated by following the change during the treatment in the pyritic phase.

Jan 1, 1976

By David B. Dreisinger

Mass and heat balance modeling is a powerful tool for the design and analysis of hydrometallurgical process flowsheets. In this first of two papers, we examine the basic fundamentals of mass and heat balance modeling, and apply these concepts to several flowsheets using a simple spreadsheet model. In this way, we aim to demonstrate how such models are not only easy to construct, but can also be indispensable for comparing various flowsheet alternatives, for making rational economic decisions, and for developing a basic understanding of existing process behaviour.

Jan 1, 2002

By K. J. Richards

The converting of copper mattes to blister copper has seen few technical advances since the introduction of batch furnaces using submerged tuyeres over a hundred years ago. The first side-blown converting vessel, operated by P. Manhes in 1882, was an offshoot of the 'Bessemer steelmaking process, and subsequent improvements in the conversion of molten mattes resulted In the Peirce-Smith converter, still the Industry standard today. While Peirce-Smith' converting has served the industry well since the early 1900!s, increasingly stringent environmental regulations, burgeoning energy costs, and a trend toward continuous processing have set the stage for a major improvement in this area of copper production. In contrast to a growing number of approaches for continuous converting using molten copper mattes, Kennecott is developing a process for treatment of solidified matte which allows improved' control, higher oxygen enrichment and a separation or decoupling of smelting and converting operations not possible with the other converting technologies. The new process known as Solid Matte Oxygen Converting, or SMOC, eliminates the need for molten matte transfers, minimizes fugitive emissions, and produces high strength SO2 off gases which substantially reduce offgas handling requirements. The SMOC process, despite additional matte solidification and size reduction steps, offers both capital and operating cost advantages for new smelters and the upgrading of existing plants, when compared with conventional converting technologies. Capital cost reductions of up to 35% in converting, gas handling, and sulfur fixation are indicated. Kennecott has successfully tested the new process concept and continued' development work is now under way to commercialize the technology. This paper reviews the limitations of batch copper converting with emphasis on the need for a continuous process, previous industry approaches to continuous converting of molten mattes, and the new Kennecott development.

Jan 1, 1983

By Dajian Wang

To obtain the thermodynamic properties of a multicomponent liquid alloy system over the whole range of concentration at an arbitrary temperature, the free volume cell theory has been applied to derive the formula of activity coefficients of liquid solutions based on the infinitely dilute solutions at some temperature. The linear logarithmic relationship between activity coefficients of binary dilute solutions and reciprocal of absolute temperature have been verified, and are in good agreement with the experimental values from the literature. The Monte-Carlo algorithm was used to calculate the nonlinear end value equations of binary systems, then the free volume parameters obtained were correlated with the activity coefficients of liquid binary, ternary, and quaternary systems at an arbitrary temperature. Three dimensional a-X-T diagrams of some binary systems representing the temperature and concentration dependence of activities were plotted. The calculated results regarding non-ferrous alloy systems have been statistically examined with the experimental values from the literature. Hence, this simple approach could be useful for analyzing thermodynamic properties of liquid alloy systems.

Jan 1, 2000

By Harald Laux, Stein Tore Johansen

The plunging jet in tapping of steel from converters or electric arc furnaces entrains gas into the steel bath contained in a ladle. Gas entrainment rate and the effect of the gas on the flow pattern in the ladle are studied by means of Computational Fluid Dynamics CFD. The work focuses on the mathematical modeling. Two numerical methods, one for free-surface flows and one for dispersed multiphase flow are combined. A transport equation for the average bubble diameter that incorporates the effect of coalescence and breakup is presented. Results from computations for one ladle and tapping configuration are shown. Our findings indicate that the gas entrainment rate is affected by the material properties of the liquid in the sense that the material properties determine the shape of the jet. Moreover, bubble sizes in the range of two-orders of magnitude are predicted in the ladle. The dispersed diameter model seems to work well. It showed the expected response to material parameters and the turbulent field. However, the presented analysis is just a first step that was limited due to certain simplifications. In order to obtain better insight in the tapping process improvements of the analysis seem necessary.

Jan 1, 1999

By Xinlei Jia, Wenming Guo, Yanling Zhang

A large amount of stainless steel dust rich in Fe, Cr, and Ni has been being generated in China. Smelting treatment is accepted as a practical method for the recovery/reutilization of these second resources, during which Fe, Cr, and Ni is reduced into one metal phase and then separated from the residue slag. Based on the typical compositions of stainless steel dust, the residual slag can be termed as CaO-SiO2-MgO-Al2O3 system. In this paper, the activity coefficients of Cr in Fe-Cr-Ni-C (-Si/Al) melt and the properties of CaO-SiO2-MgO-Al2O3- 1%CrO system thermodynamically approached. Then, in laboratory experiments, the recovery ratios of Cr and its distribution behaviors between Fe-Cr-Ni-C melt and CaO-SiO2-MgO-Al2O3 slag system were examined.

Jan 1, 2015

By Peter R. Sanford

Cyanides are present as a dilute constituent of streams from a variety of metallurgical and mineral-processing operations. In addition, a cyanide concentration in excess of approximately 100ppb is toxic to aquatic life, and consequently these operations require a waste-treatment process to reduce the already dilute cyanide species by several orders of magnitude. Furthermore, the waste streams may have flowrates in excess of a million gallons per day. The paper reports on research conducted with a laboratory?scale electrochemical porous (graphite felt) electrode (anode) flow-reactor, which was conducted in conjunction with a computer-aided simulation of a mathematical model describing the intrinsic rate-phenomena associate with the electrode processes. The laboratory-scale cell, of rectilinear geometry, was found to be capable of reducing a feed-stream anolyte (KCN-KOH and supporting electrolyte of a single salt ? K2SO4) with a cyanide concentration of 10ppm, to less than 100ppb, at current efficiencies in the neighborhood of 50%. The computer simulation of the cell performance based on the mathematical model (and constraints imposed for tractability) was found to provide only for qualitative agreement.

Jan 1, 1998

By M. A. Rabah, F. E. Farghaly, M. A. Motaleb

"Wastewater from industrial galvanization industry was reclaimed under current flow stream conditions. Results showed that the raw water contains 0.7 % by weight total suspended solids (TSS) causing turbidity amounting to 30. Measurements of Zeta potential as a function of pH revealed that solid separation takes place at pH 9. Addition of H2O2 to the polmer solution helps to oxdize ions of iron and zinc metals toinsoluble ferric oxide and zinc hydroxide to a higher state of oxidation. Addition of 5 mg/L of cationic magna flocculants polymeric solution helps the rapid separation of the turbidity. Separation of floccules so formed takes place by filtration. Addition of peroxide ions to the turbid wastewater confirms the physical stability of the flocs so formed. Impurity flocculation takes place in few seconds. Maximum temperature for safe solid removal was <30°C. The treated water was pure and safe for recycling or use in domestic purposes.IntroductionStocks and et. al. [1] show that the galvanizing process introduces spent pickling acid waste production, but its major constituent, could be used. Survey of the operational procedures adopted and the acid wastes produced by UK Galvanizers are reported. Various methods to recovery spent acid of suitable composition and to eliminate zinc contamination was considered. Application of the Kleingarn acid management system reduces waste volume, saves hydrochloric acid (HCl) and increases component throughput whilst, in conjunction with zinc elimination, could allow recycling of the majority of galvanizer’s acid wastes.Dahab [2]; Kerney [3] reported recycling of galvanizing products, including pickleliquor. Kerney suggested a mobile treatment plant for recycling pickling acids. Dahab found that pollution reduction could be achieved by relatively simple operational changes to the process that gave fairly short payback times.Rozenblat and et. al.[4] studied the extraction of zinc (II), iron(III) and iron(II) with Tributyl phosphate (TBP) from hydrochloric acid solutions containing high zinc(II) concentration. Two technological approaches for the separation are considered. Firstly, the selective extraction of iron(III) (iron(II) is oxidized to iron(III)) over zinc(II) with TBP deficiency. Secondly, iron(III) reduction to iron(II) followed by zinc(II) selective extraction with an excess of TBP. Prior stripping, the organic phase was washed with small amounts of water. Scrubbing of TBP solutions containing iron(III) contaminated with zinc(II) gives always a mixture of zinc(II) and iron(III) which must be recycled to the extraction step in continuous process. The following technological concept is proposed: reduction of iron(III) to iron(II), extraction of zinc(II) with 5-10 volume excess of TBP, washing of TBP phase contaminated with iron(II) with small volumes of water and recycling of the scrubbings and stripping of zinc with water."

Jan 1, 2008

By C. -S. Jiang

In most copper refineries, addition agents are added at predetermined rates with no further monitoring of their activity or concentration in the electrolyte. Increasingly stringent cathode quality requirements, and a desire for better process control in tankhouse operations, have recently directed a number of refineries to search for a better addition agent control strategy. Extensive development work has been carried out at the Noranda Technology Centre for the monitor in of glue and thiourea in copper refinery electrolyte using cyclic voltammetry (cv~. Data from both synthetrc and commercial electrolytes are presented, showing the ability of CV to produce reliable and easily identifiable fingerprints of addition agent concentrations in copper refinery electrolyte.

Jan 1, 1991

By Garrett May

We present a periodic technique for measuring the thermal conductivity of thin, disk-shaped samples. In samples of this type, temperature measurements must be made across the sample faces and are therefore subject to large error due to the interface resistance between the temperature sensor and the sample. The technique uses measurements of the amplitude and phase of the periodic temperature across both a reference sample and the unknown material at several different frequencies. Modeling of the heat flow in the sample allows the simultaneous determination of the thermal parameters of the sample as well as the interface resistance. The technique is demonstrated on nanocomposite samples less than 1.0 mm thick.

Jan 1, 2008

By C. J. N. Buisman

THIOPAQ technology developed and marketed by PAQUES Bio Systems in Balk, Netherlands, has been successfully used at commercial scale at the Budelco zinc refinery in the Netherlands for the treatment of contaminated groundwater since 1992. In essence, THIOPAQ technology consists of two biological process steps in series: sulfate reduction to hydrogen sulfide (anaerobic) and sulfide oxidation to elemental sulfur (aerobic). The biogenic sulfide produced can be employed for the chemical precipitation of metals in solution either inside the anaerobic reactor or in a separate vessel. Since the solubilities of most metal sulfides are much lower than of their respective hydroxides, considerably lower effluent metal concentrations can be achieved with THIOPAQ systems than in neutralization processes which immobilize metals predominantly by hydrolytic precipitation. In recent years, PAQUES has made significant advances in the design and operation of aerobic and anaerobic bioreactors for metal-sulfur systems. Moreover, the company has increased its technology portfolio to allow the development of more process oriented applications of THIOPAQ technology. A new PAQUES designed plant at Budelco treating sulfatecontaining proceswaters will be started up in 1999. The sulfate reduction is accomplished in a 500 m3 reactor in which hydrogen is used as electron donor. The endproduct, ZnS, is used for Zn and H2S04 production.

Jan 1, 1999

By B. Mishra

Calcium and lithium gallides have been synthesized by powder metallurgy techniques in the stoichiometries that can be used as reduction alloys for the Rocky Flats Plant Salt-Scrub (SS) process. The SS process is performed to recover valuable metals from salts generated in the electrorefining and the molten salt extraction processes. Combustion synthesis has been optimized for variable heating rates up to the reaction ignition temperature and for green densities of the powder compacts in terms of the ignition temperature and the exothermic heating of the product in an effort to develop LiGa and CaGaz alloys. The problems arising from the melting point and density differences of calcium, lithium and gallium have also been studied. The SS alloy compositions were produced by mixing, pressing and sintering the metal-powders. The efficiency of the intermetallic alloy, Ca-17 wt. pct. Ga, as a reductant and the effect of gallium on salt clean- up has been discussed. Measurement of actinide recovery has been studied with cerium as the surrogate for the actinide metal. The development of an alloy for SS reduces a major contaminated waste disposal problem besides recovering the valuable reactive metal.

Jan 1, 1993