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By Grégory Miette

The paper deals with a process that allows the recycling in a cupola of EAF dusts with 18 % Zn. It produces dusts with zinc grade higher than 50 - 55 % and commercial cast iron with less than 200 ppm Zn, 50 ppm Pb, 0.15 % S. The paper focuses mainly on lab tests made with the aim to develop an effective formulation of self reducing - melting pellets. With such a formulation, agglomerates develop a breaking load higher than 125 - 150 kg without any thermal treatment. Zinc and lead are volatilized in the cupola with yields higher than 95 % at 1200 OC, before any melting. Sulphur is transfemed into gas and slag. All these conditions allow to lower zinc, lead and sulphur grades below the cast iron specifications. Results of first bench scale tests performed at Fonderie Piret to validate the process will be presented.

Jan 1, 2002

By T. T. Chen

A mineralogical study of copper anodes and copper anode slimes was carried out to elucidate the silver phases present and the behaviour of silver during copper electrorefining. Most of the silver in the anodes is in metastable solid solution in the copper metal. As the copper dissolves, silver also dissolves, but is rapidly removed from solution by a variety of reactions. Some of the silver is precipitated as Ag by cuprous ions and some is precipitated as a complex CU-Ag-Pb-As-Se oxidate phase. Much of the silver, however, reacts with copper selenides to form, progressively, (CU,Ag) 2se, AgCuSe and Ag2se. The reaction commences at the periphery of the selenide grains and progresses inward; the result is commonly a silver-rich species on the outside of a silver-deficient core. Slimes collected periodically throughout the electrorefining cycle show a progressive silver enrichment of the selenides. Traces of Ag2Te also may be present, but the telluride seems to J:ie a rare constituent of most raw anode slimes.

Jan 1, 1989

By David Cocke

Study of surface and subsurface interfacial chemistry of metallic and similar systems has its enormous technological importance. Copper, for example, is a common component of many alloys and bulk amorphous systems. It is being increasingly studied today because of its use for electronic interconnect systems where processing is done below 200 ºC. Since several types of copper oxides exist, and the degree of their formation is dependent on temperature, perhaps characterization by EDS-SEM depth profiling and EIS might delineate one type of oxide from another. In this paper, we described our work on transformation of copper oxides with temperature ranging from 70 to 350 °C and their characterization by SEM, EDS, and XRD. We also showed the use of the phase angle portion of the impedance as a means to identify the predominant structure and the transition through Cu3O2 between the predominant stable CuO and Cu2O.

Jan 1, 2009

By Richard B. Diver, Mark D. Allendorf, Daniel E. Dedrick, James E. Miller, Roy E. Hogan, Andrea Ambrosini, Eric N. Coker, Anthony H. McDaniel, Nathan P. Siegel, Gary L. Kellogg

"Converting carbon dioxide and water to hydrocarbons is an attractive option for storing solar energy and, coupled with appropriate CO2 capture technology, for recycling carbon and impacting atmospheric CO2 concentrations. For any process, high solar-to-fuel efficiency is necessary for large scale viability and favorable economics. Thermochemical approaches for solar-to-fuel conversion are potentially highly efficient as they avoid the inherent limitations of photosynthesis and also sidestep the solar-to-electric conversion necessary to drive electrolytic reactions. Solar-driven two-step metal-oxide-based thermochemical cycles for producing the components of syngas, CO and H2, from CO2 and H2O are the basis of the “Sunshine to Petrol” project. Multi-cycle production of both H2 and CO has been demonstrated over several iron- and cerium-based compositions fabricated into monolithic pieces both in the laboratory and at the National Solar Thermal Test Facility. These compositions are being developed for deployment in a unique and continuous solar-driven reactor prototype, the counter-rotating-ring receiver reactor recuperator or CR5.IntroductionThe interconnected challenges posed by increasing global competition for petroleum and the increasing concentration of atmospheric carbon dioxide are now widely recognized. Meeting these challenges requires recognition that although hydrocarbon fuels are ideal energy carriers, they can no longer be thought of as primary energy sources. It is necessary to take the realistic view that our conventional fossil fuels are in fact “stored sunlight” in the form of “sequestered carbon.” This view leads to a search for options to use and store sunlight more directly.Sunshine to PetrolIn combusting hydrocarbons we unlock the energy for utilization, but we also release the carbon to the atmosphere. However, nature teaches us that with an appropriate persistent energy source, e.g. solar irradiation, it is possible to effectively reverse the combustion process and “reenergize” CO2 and H2O back into hydrocarbon form."

Jan 1, 2010

By Muhamad Firdaus

There is a growing interest in Magnetoelectric (ME) materials in view of both fundamental understanding and novel desirable applications. The application potential for multiferroic materials with the possibility of reversing the magnetization by applying an electric field (or vice versa) is quite promising especially in data storage application. The rare earth ortho-ferrites (REFeO3), such as NdFeO3, have been studied extensively in recent study in the context of discovery of magneto-electric (ME)/multiferroic nature materials. In this paper a potential high temperature recovery of rare earth elements in the form of REFeO3 from waste permanent magnets using direct oxidation in air was investigated. It was found that REFeO3 (NdFeO3) phase can be separated from the other oxide phases by thermal treatment of NdFeB magnet waste at 1100 °C in air atmosphere. The REFeO3 also found to have different physical characteristic (density) from the other layers and can be separated physically. This paper will include a proposed flowsheet to recover Nd as NdFeO3 through powder separation. The technique can be beneficial and favourable for RE recycling and recovery from waste permanent magnets.

By W. L. Dalmijn, J. M. Krowinkel

A recycling concept of end-of-life televisions starting with shredding will produce a complex material mixture, very heterogeneous in size, shape and degree of liberation. Basically all materials in television scrap are valuable, which means that recovery is important for either economic, environmental or sustainability reasons. However glass, plastics and metals are the materials with the highest potential for recovery. Non-magnetic materials from shredded television sets can be separated into three characteristic size fractions that need further separation for a high value-added recycling of the materials. This study investigated the potential of physical separation of these size fractions into valuable material streams using polyseparator, tlrldy current separator, dry and wet shaking tables and electrostatic separator. An overall mass balance of the mechanically processed televisions was calculated. Evaluation of the produced material fractions showed that heterogeneity in particle shape and size together with the presence of unliberated materials caused sever difficulties in separation when exclusively based on mechanical techniques. The results indicate that a certain degree of dismantling is necessary to achieve products of appropriate quality in physical separation. In order to improve recycling of electronic scrap through design for recycling cooperation between the electronics industry, the manufacturers and the recyclers of electronic goods is necessary.

Jan 1, 2000

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (M-f'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

Heap leaching with thiosulfate is only used in one location for the treatment of a refractory preg-robbing gold ore initially pre-treated with bio-oxidation. The chemistry of thiosulfate leaching is complex. Further work is required to develop a better control of the system. A mild refractory gold ore containing pyrite and chalcopyrite was used in this study to investigate the use of thiosulfate as an alternative heap leaching technology. Preliminary bottle rolls tests indicated that similar gold extraction was obtained with cyanide and thiosulfate. In the column leach test, effects of thiosulfate, copper and ammonia concentrations, and their ratio on both gold extraction and reagent consumption, were assessed. The range of reagent concentration were: 0.1 - 1.0M (NH4)2S2O3, 0.03 - 0.10M CuSO4*5H2O, 1.0 - 6.0M NH4OH. The solid-liquid ratio was in the range of 0.83:1 to 5: 1. Best results showed that 72% of gold was extracted in 50 days with 0.3M (NH4)2S2O3, 0.05M CuSO4*5H2O and 6M NH4OH or a combination of 1.0M (NH4)2S2O3, 0.03M CuSO4*5H2O and 3M NH4OH. The reagent consumption at solid/liquid ratio of 3:1 was 37 - 48.6 kg/t (NH4)2S2O3 and 0 - 0.62 kg/t CuSO4*5H2O. The results of thiosulfate leaching were also compared with cyanide leaching.

Jan 1, 1999

By J. Chen Kuriyama

One method to store hydrogen effectively involves the use of metal complexes such as the alkali-element aluminum hydrides. The hydriding/dehydriding properties of these materials depend on how to prepare them with different structures and microstructures. The present work focused on a high-energy ball milling technique to produce Ti-doped lithium tetrahydridoaluminate (LiA1H4) and lithium hexahydroalanate (Li3AIH6) powders with nanocrystallites. The phase structures and dehydriding/rehydriding characteristics were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller measurement, thermogravimetry, and differential scanning calorimetry. The mechanism of dehydrogenation and rehydrogenation was also examined by means of X-ray photoelectron spectroscopy (XPS). The results on the relation between the reversible hydrogen storage and catalysis function of the Ti-doped complex hydride indicate that both the homogenous distribution of Ti+AI nanoclusters and the Ti¬catalyst with Ti e> Ti3+ (Ti0/Ti2+/Ti3+) defect sites play important roles in optimizing the reversible hydrogen storage.

Jan 1, 2002

By M. L. Cunha

The lack of control of As and Sb compounds from copper smelters and converters has rendered some chalcopyrite containing arsenopyrite, stibnite and tetrahedrite minerals unusable for metal extraction. In the present investigation, we have studied the carbothennic reduction of Portuguese chalcopyrite mineral concentrate in the presence of lime/CaS04 and CaS04/Si02. Thermodynamic equilibrium calculations were performed to study the distribution of As and Sb between metal and the CaO-Si02-FeO slag phase. The phase equilibrium calculations also show the effect of oxygen partial pressure on the increase in the volume of the slag phase, which helps in lowering the copper metal formation temperature and facilitates a better separation between metal, matte and slag. The reduction reaction kinetics was studied between 850°C and 1100 °C, and the phases formed were identified by X-ray powder diffraction and scanning electron microscopy techniques. The importance of this research for using recycled matte, lean and rich minerals with As and Sb is also explained.

Jan 1, 2001

By P. Myllykoski, J. Nylander

"A commercial program package called Crownoff for the simulation of temper rolling in four high mills has been verified against measured data. The agreement between measured and calculated transversal strain distributions of the strip was found to be good. Effects of the strip crown and work roll bending force on the strain distribution were simulated. The results showed that when a single ground camber of work rolls is used for all strip widths; the strip crown should be parabolic, excluding the edge drop. An increase or decrease of the strip crown by 30 % during a coil can be compensated by a 2 to 5 t change in the work roll bending force. The ability to control the strip crown by work roll bending was insensitive to strip width. IntroductionCold rolled steel strips are usually temper rolled after recrystallization annealing, which follows cold rolling. The purpose of temper rolling is to suppress the yield point, finish the strip surface and correct possible flatness errors. The presence of a yield point might otherwise cause problems during subsequent forming processes. The in homogenous yielding in non-temper rolled steels leads to the formation of Lüders bands in the strip surface.The rolling force is influenced by the rolling speed and changes in frictional conditions in the roll bite. Therefore it is very important to plan carefully the mill settings and control algorithms during rolling. The purpose of mill control algorithms is to ensure constant reduction and the best possible strip flatness during the entire coil.Correctly predicting the rolling force is important for determining the mill presettings. Torque, forward slip and power requirements are not usually critical, if the reductions are small. However, the large elastic deformations occurring in the roll bite make the physical description of the process difficult. Physical rolling models developed for cold rolling contain assumptions that lose their validity as the reductions decrease to the level of one per cent."

Jan 1, 1994

By L. M. Abrantes, A. P. Paiva

"A brief review of some innovative methods for the direct recovery of metals from loaded organic phases is presented; emphasis is given to electroreductive stripping and cementation, which are described and illustrated by examples: of current research. The recovery of silver using a two-phase electrolysis - by direct application of an electrical potential to a mixture of a metal loaded organic phase· containing Cyanex 471X, obtained by solvent extraction, and a stabilized sodium thiosulfate solution - is more extensively discussed. The overall efficiencies are analyzed and compared with data obtained by conventional stripping procedures. Some preliminary results achieved for the recovery of the precious metal using galvanic stripping, applied directly to similar organic solutions and involving zinc and iron powders as reducing agents, are also evaluated.Introductory ReviewThe application of hydrometallurgical methods to the recovery of metal values from ores and concentrates has been receiving a growing interest, either from researchers or from the mining industry [1].For the concentration / purification of the relatively low concentrated metallic solutions resulting from the leaching of those raw materials, solvent extraction (SX) is a well established technique [2]; the loaded organic solvent is then conventionally contacted with a suitable aqueous solution, the metal in its final form being usually recovered from this solution by electrowinning.As an efficient and / or selective stripping is sometimes difficult to achieve, depending on the specific characteristics of the system under consideration, some alternative procedures have been analyzed in order to overcome this problem. One of the chosen routes, mainly developed by Hirai and Komasawa, is to promote the reduction of the desired metal species in the organic phase, in such a way that the stripping stage becomes feasible; for the selective stripping of vanadium from a solvent containing a mixture of vanadium and molybdenum, the authors successfully used reductive [3], electro-reductive [4,5] and photo-reductive [6] techniques. The two latter methodologies have also been applied to the recovery of europium from a solvent containing europium, samarium and gadolinium [7,8].However, further processing is necessary to recover the metal in its solid state; therefore, methods causing the direct reduction of the metal species in the organic phase to their fmal metallic form would be of interest, as an intermediate step would be avoided"

Jan 1, 1997

By Lin Li, Xiang Li, Yifang Zheng, Jilai Xue, Jun Zhu

"Al drops and gas bubbles in the anode-cathode space of aluminum electrolysis cell are of great importance for cell operation improvement in metal loss, current efficiency and energy consumption. A direct observation on the Al drop, gas bubble and ultrasound was carried out through a see-through cell. The Al drop immersed into the cryolitic melt was found moving up and down irregularly in the anode-cathode space without electrolysis, which was then completely dissolved into the melt. During electrolysis, the Al drop came to the anode area and reacted with the gas bubbles generated on the anode. Under ultrasound, the gas bubbles were removed from the anode surface while the Al drop was kept on the side of anode. The observed phenomena were useful for technology improvement in reducing the anode-cathode distance or lowering the energy consumption in aluminum electrolysis.IntroductionDuring aluminum electrolysis, aluminum metal drop and anodic gas bubble are in close contact each other within the anode-cathode space, and the interaction between them can produce significant impact on metal loss, current efficiency and energy consumption. The motions of the Al drop and the gas bubble are also related to the dissolution of aluminum metal into cryolitic melt and the cell voltage drop due to the bubble layer covering the anode surface.A number of studies have been carried out using different types of see-through cells, where the dissolving process of metal Al into cryolitic melts (metal fog) in the anode-cathode space was directly observed and photographed [1, 2]. With the similar method, some direct observations on the anodic bubble behaviors with and without ultrasound were performed during aluminum electrolysis [3-6]. However, to our best knowledge, there is no published work on direct observation on the behavior of Al drops and anodic gas bubbles staying together within the same anode-cathode space, as well as the motion and interaction of them in cryolite-alumina melts."

Jan 1, 2011

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (Mf'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By A. W. Bryson, K. C. Lenthall

"With the growth in the use of cobalt in industry, interest in its extraction and recovery has increased. With this increased interest comes the need for a fundamental knowledge of the processes involved in the recovery of cobalt metal. This paper examines the effects of cobalt concentration, catholyte pH, operating temperature and current density on cobalt electrowinning with respect to the current efficiency, cell potential and nature of the cobalt deposit. It is found that the cobalt concentration and catholyte pH affect the current efficiency, while current density and temperature affect the cell potential and thus the specific power consumption. Pitting on the deposit is affected by the catholyte pH and the operating temperature. Furthermore, the effect of feed flow-rate on catholyte pH, and thus current efficiency, is investigated. A model to predict the cell performance, which includes the flux of hydrogen ions through the diaphragm, is proposed.IntroductionCobalt metal is a silvery transitional metal found between nickel and iron on the periodic table. Due to its resistance to corrosion and other properties under high temperatures and its good work-hardening characteristics, it is favoured in alloys used in high temperature applications. These include aerospace, aircraft and high speed tools. Other applications include its use as a colourant in glass and ceramics, a drying agent in paints, a nutrient for livestock, a catalyst in the petroleum industry and, in the medical field, in prosthetics and radiology.The main deposits of cobalt are found in Central Africa, specifically Zaire and Zambia, although deposits also occur in Morocco, Canada and Australia. The cobalt is generally associated with other transitional metals including nickel, iron and copper. It is generally extracted by hydrometallurgical means and recovered from solution by electrowinning or hydrogen reduction. Little data [1-2] exists in literature on the electrowinning of cobalt from aqueous solutions. This paper investigates the effects of various operating conditions on the current efficiency, cell potential and deposit nature under continuous operation."

Jan 1, 1997

The U.S. Bureau of Mines investigated CaF2-assisted H2SO4 leaching to extract Mn from domestic silicate manganese resources. A pyroxmangite ((Mn,Fe)Sio3) ore containing, in pct, 34 Mn, 23 Si, 3 Ca, and 1 Fe was leached at 90° C for 3 h in a solution containing, in g/L, 12 Mn, 140 H2SO4, 130 (NH4)2SO4, and 5 CaFz. Manganese extraction of 92 pct was achieved. Manganese of greater than 99 pct purity was prepared by electrolyzing the purified pregnant solution at a current density of 50 mA/cm2. The current efficiency was 65 pct.

Jan 1, 1991

By Jay S. Gunasekera

Metal parts are traditionally processed by either filly-liquid (e.g., casting) or filly-solid (e.g., forging) state. Semi-solid metal forming incorporates elements of both casting and forging. In 1991, Gunasekera(5) developed a model illustrating the influence of flow stress by the liquid fraction. The result fits Kiuchi's (1979)(7) experimental data quite well. This model assumed the liquid part is surrounded by solid as small pockets inside the material, which is opposite to the real practical situation. Since the melting usually first happens at the grain boundary, it is better to treat the semi-solid material as small metal crystal surrounded by liquid.

Jan 1, 1997

By J. V. Atwood

The U.S. Bureau of Mines has developed a novel Double Membrane Electrolytic Cell (DMEC) that exhibits unique features for recycling contaminated metals and metal alloys. The DMEC incorporates two anionic ion exchange membranes, separating anodic and cathodic regions of the cell. The ion exchange membranes prevent significant transport of unwanted cationic impurities to the catholyte from the impure anolyte while the anion/cation balance in cell compartments is maintained through the free movement of anions between compartments. The membrane barrier makes it possible to electro refine highly contaminated materials or to electrowin from solution while utilizing alternate anode reactions. Sinceanolyte and catholyte cross contamination has been eliminated, premium cathode products are produced. The DMEC has been tested at bench, pilot, and commercial scales. Configuration of the DMEC, cell operation, scale, up efforts, and significant design factors are discussed. Two separate recycling investigations utilizing DMEC technology are presented. The first investigation examines recovery of high purity cobalt and nickel from severely contaminated super aIloy scrap. The second involves? upgrading contaminated cobalt in the U.S. Government's National Defense Stockpile. Capital and operating costs for both potential applications are presented.

Jan 1, 1995

By Sheng-li Wu, Guo-liang Zhang, Bo Su

One of the major challenges for the Canadian Gen IV Super-Critical Water-cooled Reactor (SCWR) concept is the selection of fuel cladding materials. The Canadian SCWR concept will operate at a core outlet temperature of 625 oC and 25 MPa of pressure with peak cladding temperature reaching as high as 800 oC. Corrosion resistance is an important factor for material selection. Austenitic stainless steels that contain Cr contents greater than 18 wt.% are generally considered to provide adequate corrosion resistance. In this work, the pressure dependence of the corrosion of austenitic stainless steel 310 containing 24 wt% Cr is assessed at 625 C for exposures of 1000 hours to evaluate the suitability of superheated steam as a surrogate for supercritical water at 25 MPa. Transmission Electron Microscopy (TEM) revealed that 310 exposed to different pressure conditions at 625 oC. (i.e., 0.1, 8 and 29 MPa) had generally the same type of the oxide structure, i.e., a Cr-rich oxide with the spinel structure on outer surface adjacent to the water phase. The material exposed at 8 and 29 MPa had a double layer oxide structure, with the outer oxide layer having a much larger grain size, while the samples exposed at 0.1 MPa showed only a single spinel-phase oxide layer. Cr-depleted recrystallized austenite grains were found underneath the spinel phase oxide. The adjacent large-grained austenite substrate had M23C6 carbides in the grain interior. The implications of these results are discussed.

Jan 1, 2015

By Naixiang Feng, Shaohu Tao, Zhihui Wang, Yuezhong Di

"A novel vacuum aluminothermic reduction lithium process was developed in present work which used lithium carbonate, alumina and calcium oxide as raw material. The process mainly contained three steps. The first step is that LiA102 clinker is prepared in ambient environment, then metal lithium is vacuum extracted from LiAl02 clinker with aluminum power as reducing agent, and the last step is that alumina is leached from the reduction residue with a mixture of sodium hydroxide and sodium carbonate. The results show that the lithium reduction ratio can be over 95% under the conditions of reduction temperature 1423K, reduction time 3h, and aluminum excess 20%. The main components of reduction residue are CaO· Al203 and 12Ca0·7Alz03. The alumina leaching rate of calcium aluminate in residue is over 80%. High-whiteness aluminum hydroxide can be obtained by carbonation precipitation of the reduction slag leaching solution.IntroductionWith a density about half of water, lithium is with the lowest density of all solids, mere 0.5 g/cm3 at 20 °C [l]. Lithium is widely used in aerospace, aviation, nuclear-generated power and electric battery industry. Nowadays, over 90 % of the world's primary lithium is produced by molten salt electrolysis [2-4]. But the development of molten salt electrolysis will be effected by some factors: cost, environment, and so on. Vacuum thermal reduction may be used extensively in future because of its low-energy consumption, high-purity and short-cycle."

Jan 1, 2013