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By C. M. Wai

"Metal species in solid and liquid materials can be extracted by supercritical carbon dioxide containing a suitable ligand. This in situ che1ation-supercritical fluid extraction technique offers several advantages over conventional solvent extraction including minimization of organic liquid waste generation and exposure of personnel to organic vapors. One unique feature of this technique is that metal species can be removed from solid materials directly using supercritical carbon dioxide as a solvent. Several ligand systems including dithiocarbamates, B-diketones, organophosphorus reagents, and macrocyclic compounds have been tested for metal extraction in supercritical carbon dioxide. This novel extraction technique may have important applications for metal recovery and mineral processing.IntroductionSupercritical fluid extraction (SFE) offers several advantages over conventional solvent extraction including the minimization of organic liquid waste generation and exposure of personnel to organic vapors.[1] The high diffusivity, low viscosity, and T-P dependence of solvent strength are some attractive properties which make supercritical fluids excellent candidates for extraction and recovery of organic compounds from solid materials [2] Carbon dioxide is a gas of choice for SFE because of its moderate critical constants (Tc = 31 °·C and Pc = 73 atm), inertness, and availability in purified form. After extraction, the fluid phase is depressurized to separate organic solutes from CO2 gas and the gas can be recycled for repeated use. The SFE technology has been applied to industrial scale operations such as the preparation of decaffeinated coffee and hop extracts."

Jan 1, 1996

By P. G. Comba

Many gold producing states are requiring rinsing of spent heaps to render the leached ore compatible with the environment and are placing restrictions on effluent pa, cyanide, and metals concentrations. Parameters which may affect efficient rinsing of heaps have been investigated by the U.S. Bureau of Mines in laboratory column studies. Rinse profiles for cyanide, metals, and pH as a function of the volume of water passed through the spent ore are presented. Fresh water rinsing of spent ore in columns showed that rinsing of cyanide was not affected by the rinse solution application rate. Interrupted rinsing with a rest period between applications reduced the volume of water required to meet effluent cyanide concentrations. chemical oxidation of the effluent with recycle of the rinse solutions reduced effluent cyanide concentrations and the volume of waste solution generated. Water rinsing was not successful in reducing the alkalinity of the cement agglomerated ore. A dilute acid solution had to be applied after cyanide removal to reduce effluent pa levels to specified limits.

Jan 1, 1992

By Samantha Moodley, Rauf Hurman Eric, Cevat Kucukkaragoz, Aditya Kale

"Two titania slags, rutile and synthetic rutile were chlorinated with petroleum coke and CO in a small bubbling fluidized bed reactor. The study aims to identify differences in chlorination mechanism, compare conversion rates, blowover and the chlorination of impurities for the various titania feedstocks at different temperatures.Chlorination rates were highest at 1000ºC; rutile chlorination significantly increases as temperature increases from 800ºC to 1000ºC. At 1000ºC, synthetic rutile had the highest chlorination conversion rate; this was followed by Slag B which in turn was more reactive than Slag A and rutile. The mechanism for slag, synthetic rutile (SR) and rutile chlorination differs. Synthetic rutile feed is porous, providing a larger surface area for the chlorination reaction, hence the highest conversion rates was attained. Titania slag becomes porous with the initial chlorination of FeO and MnO whilst rutile remains solid. As the porosity of slag particles increases so does its tendency to be elutriated. Ti2O3 is oxidized within the early stages of chlorination during the chlorination of FeO and MnO. Ti2O3 not oxidized is then rapidly chlorinated.IntroductionTitanium dioxide (TiO2) is the most common compound of titanium, about 95 - 98% of extracted titanium minerals is processed into TiO2 white pigment [1]. Two processing routes exist for the production of TiO2 pigments, i.e., sulphate and chloride based processes. In the chloride process, titania feedstock is fed to a fluidized bed reactor together with reductant and chlorine gas. A temperature of 1000 - 1300ºC is maintained in the reaction zone and apart from silica, zirconia, uranium and thorium, virtually all the metal oxides in the feed are converted to their respective chlorides [2]. Chlorine is recovered and recycled back to the reactor."

Jan 1, 2012

By David Dreisinger

The cyanidation of copper containing gold ores results in the co-dissolution of copper along with gold. Copper dissolution results in elevated cyanide consumption that may make the treatment of the gold ore uneconomic. Copper-cyanide species in gold mill effluents may increase the environmental toxicity of the gold mill solutions. The objective of this study was to examine the use of solvent extraction to recover the copper cyanide species from gold mill effluents. Solvent extraction with Cognis (formerly Henkel) reagents LIX 79 and LIX 7950 was studied. Excellent extraction of copper and cyanide was achieved using pH control in extraction. Copper and cyanide may be stripped from the reagents using basic eluants. Various routes for copper and cyanide recovery from the strip solution were studied. Excellent results were obtained using electrowinning in both divided (Nation membrane) and undivided cells. Cyanide recovery was obtained by AVR treatment of a bleed stream from electrowinning. Full results of solvent extraction, copper and cyanide recovery are reported.

Jan 1, 1998

By S. I. Sobol

Completeness of cobalt recovery from slag requires decomposition of maggemite and non - ferrous metal desorption with polymerized silicon-acid. Cobalt losses are reduced in leaching tai1s up to 200 g/t of iron.

Jan 1, 1993

By J. S. Kirkaldy

A theoretical procedure is demonstrated for calculating two-dimensional binary cellular single-valued interfaces and extended to triple-valued (remelt) shapes. The numerical calculations for the single-valued local equilibrium problem which yield unique shapes as functions of the supersaturation parameter a and the partition coefficient k are reviewed. The cell amplitude L and wavelength A scale identically as the inverse velocity to the 112 power and the aspect ratio r is a constant equal to 312, independently of a and k for a < 0.5.. For 0.5 < a < m, L, A and r decrease asymptotically to zero indicating the finite amplitude nature of the instability at a = 1 and the existence of sub-marginal states which converge to a flat interface at a- m (Glv- m). Scaling comparisons between equilibrium single-valued and triple-valued and deep-rooted non- equilibrium cells are made.

Jan 1, 1992

By M. Misra

Acid mine drainage from reactive sulfide tailings is a major environmental concern facing the mining and mineral industries. A preventive technique to control acid mine drainage by agglomeration and encapsulation process is presented in this paper. The reactive tailings are agglomerated using Portland cement type I1 as binder. The cold bonded agglomerates after specified curing period are, strong and resistance to weathering. The leaching and weathering experiments have shown that a significant reduction in the concentration of dissolved metals can be observed with the agglomerates as compared to as- received tailings. Addition of small amount of sodium silicate during agglomeration increases the strength and develop good resistance to weathering by forming a glassy coating and elongated crystals within the agglomerates.

Jan 1, 1993

By Ehsan Khajeh

In this study, the permeabilities of Al-15.5wt%Cu and Al-19.5wt%Cu have been determined by solving the full Navier-Stokes equations on 3D geometries of interdendritic channels obtained by X-ray microtomography (XMT). The samples for XMT were sectioned from different positions in directionally solidified cylinders in order to obtain a variety of microstructures for each composition. The flow has been solved using a 2nd-order accurate Finite Volume Method (FVM) approach. The effect of employing uniform or unstructured mesh on the calculated permeability has been studied. The Marching-cube triangulation method was necessary to extract accurate surfaces for unstructured volume meshing. Calculated values of permeability for this range of solid fractions show partial agreement with previous experiments. Observed deviations are attributed to the difficulties of experimental permeability measurements.

Jan 1, 2009

By B. J. Jody

At Argonne National Laboratory, we have been developing a potentially economical process to recycle automobile shredder residue (ASR). We identified three potentially marketable materials that can be recovered from ASR and developed technologies to recover and upgrade these materials. We built and tested a field-demonstration plant for recycling polyurethane foam and produced about 2,000 lb (907 kg) of recycled foam. Several 300-lb (I36-kg) samples were sent for evaluation and were found to be of marketable quality. We are also preparing for a large-scale test in which about 200 tons (181 tonnes) of ASR-derived fines «0.25 in. [<0.62 cm]) will be used as a raw material in cement making. A major cement company has evaluated small samples of fines prepared in the laboratory and found that they meet its requirements as a substitute for iron ore or mill scale. We also produced about 50 lb (23 kg) of recycled acrylonitrile butadiene styrene (ABS) from obsolete automobiles and found that it has properties that could be readily upgraded to meet the specifications of the automotive industry. In this paper, we briefly discuss the process as a whole and summarize the results obtained from the field work on foam and fines recycling.

Jan 1, 1996

By A. V. Tarasov

The proposed process is based on creating a controlled frothed layer of molten slag, in which fine particles of carbonaceous reductant and raw material to be processed are mixed with emulsified iron. Frothing of the slag layer without external blowing occurs as a result of intensive evolution of gaseous reduction products. The froth reaction process is maintained due to the heat of an electric arc in the slag layer. When the metal bath is heated by the arc to 1400- 1 500°C, the low temperature of the slag surface of about 1200-1 300°C is maintained due to low thermal conductivity of slag froth preventing heat loss. In order to maintain the required slag froth level and control the process temperature, air tuyeres are installed above the slag bath; blowing air serves also for oxidation of zinc in fumes and for its transportation. High adsorption and thermal insulating properties of slag froth ensure virtually complete elimination of dust and mist entrainment along with low heat losses. The main macrokinetic regularities of the carbon thermal reduction of zinc-containing slag melts have been studied under frothing conditions. The mechanism of formation of gas-slag emulsion has been identified under the conditions of reaction [C]+[O]=CO occurring locally at the slag-metal interface. It has been demonstrated that under the froth reduction conditions the zinc removal rate from the melt increases on the average by 3 to 5 times. Based on the physical and chemical data obtained, basic principles of the dezincing technology have been developed for different intermediate oxide iron-containing products produced in the process of ferrous and non-ferrous metals production.

Jan 1, 2002

By Marcio Toshio Tanaka, Marcelo Breda Mourao, Cyro Takano, Cesar Yuji Narita

"The concerns in questions related to the environmental impact in the steelmaking industries caused mainly on the gas emissions such as the dioxide carbon are due to its raw material such as the coal, a fossil and non renewable resource. The purpose of this paper is to replace from 10% to 50% of the coal used in cokemaking by mixing it with a renewable source (wood charcoal). The powder (- 325 mesh) from both raw materials (coal and wood charcoal) were mixed in order to obtain a briquette that was then heat treated at 1100°C to obtain the biocoke. Results of usual analysis (coke reactivity index, coke strength after reaction and cold crushing strength test) were employed to compare to regular coke briquettes. It was found that biocoke with different amounts of wood charcoal present features enabling it to be used in some ore reductionprocesses.1. IntroductionThe iron and steelmaking industry is a heavy emitter of carbon dioxide; according to the World Steel Association, 6.5% of global emissions of this greenhouse gas is due to the production of ferrous materials [ 1]. This is due to the fact that the fuel and reductant employed in the blast furnace is metallurgical coke, obtained from fossil coal. There are some projects aiming to reduce or even eliminate the emission of fossil GHG in the iron and steelmaking process [2]. Most of them propose the capture and storage of the gas (CCS) [3], a technology not yet proven. Other studies point out that the coke consumption in the blast furnace could be reduced by using high reactivity coke; this could lead to lower temperatures in the thermal reserve zone of the blast furnace and consequently less fuel rate in the furnace.The use of biomass in the iron ore reduction process is known as an environmentally accepted solution, as biomass does not release already fossilized carbon."

Jan 1, 2013

By Masayuki Kudoh, Tohru Maruyama, Yohichi. Ito

When hypo-peritectic carbon steel is quenched during unidirectional solidification, the region of fine columnar grain is observed. It is classified into two coexisting phases. One is coexisting phases of liquid, delta and gamma in the upper part of the region, and the other is coexisting phases of delta and gamma in the lower part of the region. To form the coexisting part of the three phases means that solidification in this experiment proceeds in non-equilibrium state. The size of the narrow side of one fine columnar grain coincides with the arm spacing of a primary dendrite and this result is the same as the hyper-peritectic carbon steel. However, the boundary of the fine grain in the hypo-peritectic carbon steel is formed in different location from that of the hyper-peritectic carbon steel. The former is formed in the skeleton of the dendrite, while the latter is formed in the interspacing of the dendrite. The region of the fine grain changes suddenly to that of the coarse grain when the delta phase in the coexisting part of two phases disappears completely. Therefore, the delta phase in the hypo-peritectic carbon steel might prevent the growth of gamma grain. In order to recognize it, ferrite formers such as Mo, V and Ni are added in the sample. Then, the longitudinal length of the fine columnar grain extends in the sequence of the no addition, Mo, V and Nb.

Jan 1, 2000

By Gordon A. Irons

"Powder injection for melt refining is widely practiced in the steel industry, and is gaining acceptance in the non-ferrous industries. In these commercially-important systems, the thermodynamics and kinetics may be very complicated. More than one element may be removed by refining, and often the refining agents are not just one compound. In this paper, the thermodynamic and kinetic aspects of these processes are reviewed. A number of examples are given, such as the desulphurization of iron with a variety of reagent mixtures, and selenium removal from copper with several different reagent combinations.IntroductionI am very pleased and honored to present a paper at this Symposium recognizing the many contributions of Professor Howard Womer. Even at the time I was an undergraduate student, the WORCRA process was part of the curriculum. I remember at the time that I was fascinated by the concept, and due to it and the many other rapid developments in Process Metallurgy, I chose it as my field of study. I think the Symposium is testimony that Professor Womer has touched the lives of many others as well.My original assignment was an overview of the basic aspects of gas and solids injection. However, I reviewed most of this material at the Savard/Lee Symposium [1]. In the present paper, I will present some of the basic issues related to refining with powder injection, using work that we have recently completed in both ferrous and non-ferrous systems."

Jan 1, 1996

By Y. A. Chang, J. Woodford, C. R. Kao

Reactive diffusion studies between NbC and Si were carried out at 1300 °C under a vacuum of 10-5 torr and a uniaxial pressure of 1 MPa. The annealing time ranged from 8 to 100 hours. The Si used was single crystal silicon; the NbC was hot-pressed powder compact. A NbSi2+SiC two-phase reaction layer formed with NbSi2 as the matrix and SiC as discontinuous particles. The microstructure of the reaction product is homogeneous, dense, and fine. The NbSi2 grain size and SiC particle size are in the micron range. The growth of the reaction products follows parabolic kinetics. Extrapolation of the data to zero thickness suggests an apparent incubation time of 3.5 hours. However, for short annealing time «60 hours), the thickness data can be approximated by linear kinetics with an initial growth rate of about 2 11m/hr. Based on these experimental observations, a growth mechanism for the reactive diffusion between Si single crystal and NbC powder compact is proposed. We propose that the nucleation sites for the SiC particles are at the voids of the NbC powder compact. This proposed nucleation mechanism offers a potential way of controlling the SiC particle size by changing the void size and void density of the NbC powder compact. This hypothesis, if proven to be true, will allow us to control mechanical properties of the composites by tailoring the SiC particles formed. It is also pointed out that the microstructure requires Si to be the dominant diffusing species and to diffuse through the reaction layer, while Nb and Conly have to undergo local rearrangement.

Jan 1, 1996

By E. A. van Dijk

Dusts from steel-making processes contain substantial amounts of zinc. Such dusts are also a hazardous waste and dumping them becomes unacceptable from environmental point of view. Therefore processes that can recover zinc and possibly other metals from steel-making dusts are being investigated. The aim of this paper is a contribution to the more fundamental kinetic aspects of zinc reduction from silica free calcium ferrite slags. The effects of alumina, lime and magnesium oxide contents of the slag, the COICO, ratio and the effect of initial Fe2O3/CaO ratio were studied experimentally at 1400°C The results indicated that the reduction of zinc from molten slag was possibly a first order reaction. As expected higher COICO, ratios increased both the extent and the rate of reduction. It was also observed that a higher iron content of slag improved the reduction of zinc from calcium ferrite slags. This fact seems to support the proposed mechanism that zinc is partly reduced by ferrous iron to zinc vapour and that ferric iron is reduced by carbon monoxide. The reduction rate of zinc in these slags was decreased by increasing alumina content of the slag. Alumina decreased the calculated optical basicity of the slag showing the fact that reduction of zinc oxide was more favorable in more basic slags. Probably the formation of complex ions by alumina and zinc oxide such as ZnAl2O32+ lowers the activity of Zn2+ ions in the slag and hence render them more difficult to reduce.

Jan 1, 1999

By Lifeng Zhang

The transport of fluid, heat and particles (bubbles and solid inclusions) in flowing molten steel is investigated in steel refining ladles, the continuous casting tundish, continuous casting mold and strand, and steel ingot casting processes. Inclusion removal from the molten steel by flow transport and bubble flotation, and inclusion growth by collision and diffusion are discussed. Removal of impurity elements such as [C] and [O] during steel refining are reported.

Jan 1, 2006

By H. Itou, J. M. Toguri, T. Takasu

"Marangoni convection has a large effect on materials processing since it remarkably enhances heat and mass transport near a free interface. To have a better understanding of the behavior of Marangoni convection in molten salts, observation and calculation of the thermal convection in a column held between a pair of Pt disks (2mm in diameter) fixed to hot thermocouples, were carried out.Calculated flow patterns and absolute values of fluid velocity agreed well with the observed results. When the temperatures of both disks were set equal and the height of liquid column was 2.4mm, four vortexes were generated on the longitudinal plane with a typical velocity of 15mm/s . From the calculated isothermal lines, the behavior of the enhanced heat transport was obvious; fluid heated at the disks was conveyed to the free surface and the cooled fluid at the surface was conveyed to the inner region. Increase in the height of column and/or increase in the absolute value of applied temperature difference lead to increase in fluid velocity lineally in this calculation range.IntroductionIn the processing of many materials, fluid flow of melts has a large effect on refining capabilities and on the characteristics of the produced material. Marangoni convection is generated when a spatial gradient of interfacial tension exists on the free interface due to differences in temperature and/or concentration. This promotes heat and mass transfer locally near the interface.For example, Marangoni convection which are created following the dissolution of interfacially active materials, increases the local corrosion rate of refractories (1-3). In absorption and discharge of oxygen and/or nitrogen in a molten metal, the effective reaction rate of the gas components through the gas-liquid interface increases (4-7). Also in crystal growth, the distribution of defects and impurities in the crystal is affected and this can alter its quality (8-11 ). The temperature distribution is also affected and can greatly change the productivity. For these reasons, the effectiveness of Marangoni convection in refining should be quantitatively clarified and its control should be better understood."

Jan 1, 1997

By Matthias Merzkirch, Volker Schulze, Kay Andre Weidenmann

"Unidirectionally reinforced light weight compounds based on light metals such as the aluminium alloy EN A W-6082 are adequate materials for the future use in transportation means like automobiles and airplanes. Due to the occurring cyclic loads knowledge about the crack growth behaviour of such composites is needed. The investigations at a load ratio of R = 0.18 show that the crack growth rate of the aluminium matrix is reduced if reinforced by spring steel wire with a reinforcing ratio of only about 1 Vol.-%. Additionally, the acoustic emission analysis allows detecting crack growth within the matrix material, crack propagation along the interface wire/matrix and crack closure which could also be determined with the help of a self designed capacitive displacement measuring gauge. The damage behaviour could be verified by metallographic and SEM investigations.IntroductionIn the field of lightweight structures for transportation means the need for light, strong and stiff materials, in particular composite materials, is increasing in order to save resources and costs. Lightweight materials such as aluminium and magnesium alloys are highly efficient candidates to be used in the composite extrusion process [1] which allows for a simple production of unidirectionally reinforced profiles with a large diversity of geometries at low costs. Figure 1 depicts the principle of the composite extrusion process; within the first part of the tool the billet material is split into several strands whereas the middle part of the tool allows the supply of the reinforcing elements. The third part of the tool rejoins the matrix material and the reinforcing elements and defines the final shape of the profile."

Jan 1, 2011

By Kazuhiro Nisizono, Takashi Kuroki, Nobuyuki Mori, Keisaku Ogi

"The improvement of critical current density and mechanical property is essential to the practical application of the superconductive oxides. A solidification technique is developed in this study for the growth of columnar or single Y123 crystal with finely dispersed Y211 and Ag particles through a monotecto-peritectic reaction of Li.(Ba-Cu-Ag-0 rich liquid)+ Y211-+ Y123+Lz(Ag rich liquid). The large solidification rate and temperature gradient can refine the Ag and Y211 particles. But Ag-free region is widely formed along the crystal growth direction in the central part of the Y123 cell. Since this phenomenon occurs because of the cellular growth, it is necessary to narrow Y123 cell width or to grow Y123 crystal with flat freezing interface. By controlling crystal growth direction using a seed crystal, Y123 columnar or single crystal with uniformly dispersed fine Ag particles are obtained. The· behavior of Ag and Y211 particles during the solidification of Y123 crystal is simulated by the peritectic growth model of faceted Y123 crystals.IntroductionY-Ba-Cu-0 superconducting oxide (YBCO) with high critical temperature also has excellent superconducting characteristic under the high magnetic field. The critical current density (Jc) has been enhanced by ·using unidirectional-solidification technique, which can overcome the weak-link problem at grain boundaries and control the crystal orientation and the distribution of Y211 particles which give effective magnetic flux pinning centers in the Yl23 matrix [1-4].In addition to improving superconducting properties, it is necessary to improve mechanical property for the practical application. The silver addition to the melt-textured YBCO superconducting oxide has been reported as the effective method to improve mechanical properties without degrading superconducting properties. Since the material properties are considered to be largely affected by silver particle size, form, dispersion state etc. in the Y123 phase, it is important to control Ag distribution in YBCO/Ag composites. Besides, it is also reported that the silver addition improve the corrosion resistance to the water and CO2 [5,6]. Nishizono et al. [7-9] have reported that the silver distribution in the YBCO/Ag composites is largely affected by the solidification condition, but yet some unclear points are also remained. YBCO has been also fabricated by the zone melting method [10-12], and Furuya et al. [5] and Hirano et al. [13] have reported the fabrication of silver added YBCO composites, but the distribution and behavior of Ag are not investigated in detail"

Jan 1, 2000

By C. Acuna

The standard procedure of fire refining consists of sulphur removal via air injected through tuyeres, arsenic slagging via soda-lime flux and oxygen reduction by air or oxygen deficient air or a steam fuel mixtures. The use of porous plugs to stir with an inert gas has been mainly considered as a surface renewing agent that increases the product quality and shorten the refining cycle. In the present study the effect of the bottom stirring by nitrogen gas injection through porous plugs for the treatment of the crude copper in the range of 400-150 ppm sulphur, 3,000?2,000 ppm arsenic and 14,000-7,000 ppm oxygen content was investigated. The combined effect stirring-reducing, by the use of air or a steam fuel mixtures through tuyeres for oxygen removal, follows a kinetics of first order where the constant, K, can be represented by the following polynomial expression: K = A .* R2 + B * R + C Where A, Band C are constants that depend on the nitrogen flow rate and R is the air-fuel ratio or the steam-fuel used in the reducing step. Depending on the optimization of the flow of nitrogen and the air-fuel or steam-fuel mixture and only if just the oxidation, complexing and reducing steps are considered, the process cycle might be shortened by 45%.

Jan 1, 2003