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By Ehsan Vahidi, Fereshteh Rashchi, Ataollah Babakhani, Alireza Zakeri

"The synergistic effect of Cyanex 302 on solvent extraction of nickel and cadmium from sulfate solution with D2EHPA diluted in kerosene was investigated with the aim of increasing separation efficiency. Experiments were carried out within a pH range of 0.1-5.0 using sole D2EHPA and D2EHPA-Cyanex 302 mixtures in different ratios. Increasing Cyanex 302 to D2EHPA ratios in the organic phase caused a left shifting of the extraction isotherm of cadmium and a right shifting of the extraction isotherm of nickel. As a result, optimum separation was found with a Cyanex 302 to D2EHPA ratio of 0.1M:0.5M. In the present system, effect of a modifying reagent such as TBP was studied. The influence of various diluents including kerosene and carbon tetrachloride was also investigated.IntroductionBatteries are popular sources of portable energy. Ni-Cd batteries are manufactured in two main groups of small domestic cells and large industrial batteries with 80% being in domestic use. Ni-Cd cells have various uses, for example in cordless electric utensils, cordless telephones, airplane engine starters, and communicational distribution systems [1].Depleted Ni-Cd batteries are classified as hazardous waste since nickel and cadmium are heavy metals and suspected carcinogens. Given the risk associated with uncontrolled disposal, directions for issuing legislation on disposal and recycling of used batteries have been made in industrialized countries [2]. Recycling of Ni-Cd batteries is important from both economic and environmental points of view. Different methods have been used for recycling these wastes through pyrometallurgy [3], biotechnology [4,5], and hydrometallurgy [1,2].Due to the advantages of hydrometallurgical processes, several studies have been implemented on leaching and solvent extraction (SX) of the used Ni-Cd batteries. Leaching of batteries is usually done in sulfate or chloride media; while solvent extraction has been used in different extractants: two-stage solvent extraction by D2EHPA and Cyanex 272 [6]. Solvent extraction of Cd from leach solutions has been studied using various extractants; Cyanex 301 [1], D2EHPA [7], Cyanex 302 [8], Cyanex 923 [9], Cyanex 272, Tops 99, PC88A [10]. Application of phosphorus based extractants for the solvent extraction studies of Ni such as TOPS 99 [11], D2EHPA [12], Cyanex 272 [2], has been investigated. Separation of Cd(ll), Ni(II), and Co(ll) from chloride leach liquor of spent batteries [13], were explored in the earlier studies. Cd extraction with D2EHPA involves co-extraction of both Ni and Co [14], which causes issues in the separation process efficiency."

Jan 1, 2012

By Bruce W. Wessels

"Metal-organic chemical vapor deposition has been shown to be a highly versatile technique for the synthesis of complex oxides. High dielectric constant oxide thin films of SrTiO3, BaTiO3, Ba1-xSrxTiO3 and SrxBa1-xNb2O6 can be be be deposited at 800 ºC with this technique. The fluorine substituted B-diketonate precursors have been shown to be well-suited for the deposition of high quality, epitaxial thin films of these materials.IntroductionThere has been a resurgence of interest in thin film ferroelectric oxides as a result of the development of techniques to deposit high quality material. Both physical and chemical vapor deposition techniques have been realized. Of the chemical vapor deposition techniques, metal-organic chemical vapor deposition (MOCVD) has received the most interest for the deposition of ferroelectric oxide thin films. This results, in part, from the availability of a number of volatile metal-organic precursors.(l) Moreover, MOCVD offers the advantages of high growth rates, uniform coverage over large areas, conformability, abrupt interfaces and excellent epitaxial crystallinity. Of the metalorganic precursors, the B-diketonate complexes have played an important role especially in the deposition of ferroelectric oxides containing alkaline-earth metals such as BaTi03 and Ba1•XSrxTi03. For example, barium tetramethylheptanedionate Ba(thd)2 has been used in the preparation of BaTi03 by MOCVD.(2) These compounds, however, are not without their problems. Ba(dpm)2 has a relatively low volatility; and as a consequence, temperatures in excess of 180·C are required for volatilization. This leads to the necessity of a complex precursor delivery system to insure that the precursor does not condense before the reaction zone. Moreover, the Ba precursor tends to oligomerize leading to a decrease in vapor pressure as well as a problem with reproducibility. To counter these problems, novel liquid source and solid source precursor delivery systems have been developed. (3)(4)"

Jan 1, 1994

By Pragna Bhakta

Newmont has investigated potential treatment options for low-grade refractory gold ores since 1988. After extensive R&D at Newmont?s laboratories, biooxidation pretreatment followed by ammonium thiosulfate leaching was selected for application to sulfidic preg robbing ores. A heap biooxidation and ammonium thiosulfate leaching demonstration facility was constructed in 1995 to conduct large-scale pilot tests at Newmont?s Carlin Operations. This paper presents Newmont?s experience with the recovery of gold from preg robbing ores using ammonium thiosulfate.

Jan 1, 2003

By Corby G. Anderson

Over the past 15 years, numerous pressure oxidation plants for pretreatment of gold ores and concentrates have been installed throughout the world. While this technology is now established, it suffers in terms of the complex engineering and operational characteristics inherent in utilization of high temperatures (i.e. up to 225oC) and high pressures (i.e. > 3000 kPag). This paper outlines the application of an industrially proven pressure leaching methodology utilizing nitrogen species catalyzed pressure leaching and alkaline sulfide gold leaching. As such, it stands as an economic and engineering advancement in pressure leaching and non-cyanide treatment of gold ores and concentrates. In particular, the technology offers significant technical and economic advantages over traditional pressure oxidation and cyanide gold recovery in the treatment of gold bearing chalcopyrite ores and concentrates. An example of this will application will be delineated in this paper.

Jan 1, 2003

By E. Morrice

Solubility of yttrium oxide (Y203) in fluoride melts was experimentally measured in the temperature range of 998 to 1273 K and, YF3 composition in LiF.YF3 melts varying from 20 to 50 mole pct using a graphite crucible in an argon atmosphere. Solubility of oxide in the melt was found to increase with increasing temperature and YF3 composition in the melt. An expression for in XY2O3 as a function of temperature for several melts was deduced. The calculated activity coefficients of Y2O3 in the melts exhibited a negative deviation from Raoult's law.

Jan 1, 1989

By Giovanni Principi

The activity of the ?Hydrogen Group? of Padova University, addressed to the study of materials for solid state hydrogen storage, is illustrated. Various Mg-based materials have been considered and are being studied: a) MgH2 and 0.5% mol Nb2O5 mixture ball milled under argon atmosphere; b) Mg-Ni-Fe intermetallic compounds prepared by short time ball milling of ribbons obtained by melt spinning and by long time ball milling of a mixture of MgH2, Ni and Fe powders; c) MgH2 ball milled in argon with Mm-Ni-Al (Mm = La-rich mishmetal) and Zr-Cr-Fe catalyst alloys. All the samples have been structurally characterized by X-ray diffraction (Rietveld refinement) before and after hydrogen absorption/desorption cycling and tested with a Sievert apparatus as regarding their thermodynamic and kinetic properties.

Jan 1, 2006

By M. Hashiuchi

In 1972, the tankhouse of the Tamano Smelter adopted a high current density electrolysis operation applying the PRC (Periodic Reverse Current) method. In 1994, the phase four production expansion project, which incorporated significant re-structuring of the organization, was completed and we have achieved an annual production capacity of 191,000 tons. The target of this project, the production capacity, was increased by 1'8% and labor productivity by 25%. After the expansion, some improvements in the starting sheet section and the verticality of the electrodes were carried out, and the efficiency of the operation was greatly enhanced, including the improvement of the quality of the electrolytic copper.

Jan 1, 1999

By C. Anderson

Most applications of copper metallurgy are geared towards primary production. However, as recycling of materials is a growing industry, one future facility will rely on copper metallurgy as a means of processing precious metals. This paper will discuss the derivation of the proposed copper pyrometallurgical and electrometallurgical unit operations to be utilized in industrial recycling of secondary precious metals.

Jan 1, 1999

By A. H. -J. Siegmund

Since the last survey of lead smelters in 1987, the lead industry has experienced many changes. Technological innovations, in combination with a dramatic shift in the market structure as well as more stringent government regulations, caused major upheavals in many different areas. Therefore, a new survey was performed to review the progress in the technology of lead recovery over the least decade. The newly conducted survey reflects all current phases of the world's primary lead production, from charge preparation to refined metal shipment. It was prepared by sending questionnaires to individual companies, and the detailed statistical data of this survey are presented. In considering the data developed from the survey, it should be recognized that the primary lead industry is at a crossroad where novel technologies will gradually substitute the sinter machine - blast furnace operation in the new millennium.

Jan 1, 2000

By Murray Johnston

New measurements have been made on the equilibrium distribution of selenium and tellurium between molten slag and metal phases. Distribution coefficients of Se and Te between magnesia-saturated calcium ferrite slag and copper or silver alloys were measured over the temperature range 1473 and 1673 K under controlled oxygen patrial pressures of 10-11 to 10-0.68atm. The results demonstrate that the minor elements are present in the calcium ferrite slag as the selenide (Se2-) and telluride (Te2-) respectively, up to a PO2 of 10-6 atm. As conditions become more oxidising, Te undergoes a transition to the divalent oxide whereas Se does not. Increasing the temperature was found to enhance partitioning of the minor elements to the slag. In terms of activities, at 1573 K, Se showed strong negative deviation from the ideal behaviour in the slag, while Te showed only slight positive deviation.

Jan 1, 2006

By Corale L. Brierley

Bioheap leaching, commercially applied for secondary copper ores and agglomerates, is rapidly gaining popularity. Bioleaching of chalcopyrite concentrates is imminent. Copper bioheap leaching encompasses the bioleaching of acidified and agglomerated coarse, secondary copper ore, stacked on permanent or on/off pads. The stacked ore is irrigated with raffinate containing bacteria. LME-grade cathode copper is produced by SX/EW. Low capital and operating costs, rapid start-up, environmental benefits, operational simplicity and a good performance record make bioheap leaching an attractive technology. This paper looks at the state-of-the-art of copper bioheap leaching and chalcopyrite concentrate leaching, the risks, the benefits, costs, bioheap performance and the future prospects of copper bioleaching.

Jan 1, 1999

By Takao Mori

Novel rare earth boron icosahedral compounds are investigated as potential high temperature thermoelectric materials. REB50-type compounds and REB22C2N compounds were synthesized and the thermoelectric properties measured. Seebeck coefficients in excess of 200 V/K are observed at temperatures above 1000 K for the REB50-type compounds. Strikingly, n-type behavior was observed for REB22C2N. Up to now, non-doped B12 icosahedral compounds have all been p-type. The discovery of an n-type compound is extremely important in terms of the potential development of this class of compounds as viable thermoelectric materials. Low thermal conductivities of < 0.03 W/cm/K at room temperature was observed for these rare earth boron cluster compounds.

Jan 1, 2006

By Shinya Hodoshima

A catalysis pair of tetralin dehydrogenation / naphthalene hydrogenation has been proposed in the present paper as a liquid organic hydride for operating stationary fuel cells. Catalytic naphthalene hydrogenation, having been commercialized since the 1940s, proceeds to generate decalin via tetralin as an intermediate. The storage capacities of tetralin (3.0 wt%, 28.2 kg-H2 / m3) are lower than decalin (7.3 wt%, 64.8 kg-H2 / m3) but both tetralin dehydrogenation and naphthalene hydrogenation are much faster than the decalin / naphthalene pair. Moreover, existing infrastructures such as gas stations, chemical tankers and tank lorries are available for storage, transportation and supply of hydrogen. With respect to the stationary fuel cells with large space for hydrogen storage, tetralin as a hydrogen carrier is superior to decalin in terms of fast hydrogen supply or power density. Rapid hydrogen supply from tetralin under mild conditions was only accomplished with the carbon-supported metal catalysts in the ?superheated liquid-film states? under reactive distillation conditions. In contrast to the ordinary suspended states, the catalyst layers superheated in the liquid-film state gave high catalytic performances at around 250OC. As a consequence, both serious coke formation over the catalyst surface and excessive consumption of exergy were prevented simultaneously.

Jan 1, 2006

By Ian M. Ritchie

Cementation or metal displacement reactions such as Cu2+ + Fe Cu + Fe2+ are among the oldest known hydrometallurgical reactions. They are still used in the recovery of some metals and in the purification of process liquors and waste water streams. However, they are often more complex than the stoichiometric reaction would suggest because they involve the simultaneous deposition of one metal onto a second which is dissolving. For example, sometimes a cementation will not take place, even though it is thermodynamically favoured. On other occasions, a cementation reaction will start but come to a halt as the depositing metal blankets the reacting surface. On yet other occasions, side reactions, catalyzed by the deposit, can be important. In this paper, the electrochemical basis of cementation reactions is described. The conditions for each of the complications encountered in these reactions are described and illustrated by examples drawn from a number of hydrometallurgical processes. The cementation reaction between activated carbon and gold thiosulfate is also briefly described, this reaction being unusual in that no dissolution of the carbon occurs.

Jan 1, 2003

By Kwang-suk You

This paper describes the characteristics of electric arc furnace slag (EAF slag) as an aggregate of concrete along with the chemical composition, leaching concentration of heavy metals, the soundness of EAF slag and compressive strength of mortar with 20% and 50% replacements of sand. The results showed that leaching of heavy metals and soundness of EAF slag satisfied Korean environmental limit and Korean Industrial Standard for aggregates. The compressive strength of mortar increased as the replacement ratio of EAF slag for sand increased.

Jan 1, 2006

By M. Kawakami

In the blast furnace, the reduction of iron oxide and gasification of coke occur simultaneously. It is well accepted that the gasification reaction controls the simultaneous reaction. Therefore, it is important to develop highly reactive carbonaceous materials. It is also known that the reaction is accelerated catalytically with the addition of some materials. In the present work, the catalytic effect of iron, nickel and CaO on the gasification of graphite and coke was examined. The catalytic effect of iron, nickel and CaO on the reaction rate of graphite was noticed The effect was larger at lower temperature. At 1373 K, the effect almost vanished. The effect was larger in the order of CaO, iron and nickel. The reaction rate of de-ashed coke increased by the addition of iron and nickel. The effect of iron was larger than that of nickel. The effect was larger at higher temperature, which was contrary to the case of graphite. The reactive surface area increased also by the addition. Therefore, the catalytic effect on reaction rate might be attributable to the increase in the reactive surface area.

Jan 1, 2006

Most of the world's zinc metal is produced via the roast- leach-electrowinning (RLE) process. The process is well established, but most of the sulphur in the sphalerite concentrates reports in the acid, which has to be stored and/or sold. There are significant incentives to develop a simpler process with much reduced acid generation. Ferric ion is a well known oxidant for most sulphides, in particular sphalerite, and it converts the sulphide to elemental sulphur. Based on stoichiometry, however, the amount of ferric ion needed to achieve acceptable zinc extractions is prohibitive for downstream zinc recovery from the leach solutions. The process suggested here makes use of less-than-stoichiometric ferric sulphate additions because the ferric ion is regenerated by sparging SO2/O2 mixtures. This regeneration can be effected in-situ in the leach vessel or outside the leach vessel. An example of the application of this new process is presented for a Canadian sphalerite concentrate assaying 60% Zn. The effects of temperature, ferric concentration and ferric ion regeneration are presented. Options to recover zinc from the leach solution are also briefly discussed.

Jan 1, 2000

By D. J. Sellmyer

This paper is Intended to review recent developments in the application of rare earth-transition metal alloys as high density, rewritable data-storage media. First generation magneto-optic media are based on amorphous Tb-FeCo or GdTb-Fe alloys which are adequate but could use improvements In certain respects. A very difficult materials-design problem is encountered because of the following requirements: a sufficiently large Intrinsic uniaxial anisotropy, a Curie temperature in the range 100-300°C, a sufficiently high coercivity, a sufficiently high optical absorption, a high Kerr rotation, reflectivity and high carrier-to-noise ratio, a high storage density, a very fine and homogeneous nanostructure, long-term stability, and inexpensive production. , Fundamental issues such as the relationships between the nanostructure and perpendicular magnetic anisotropy, and electronic structure and Kerr rotation are discussed. Attempts to tailor the properties by rare-earth alloying and by preparing compositionally-modulated, nanostructured multilayers are outlined. Challenges and opportunities in competitive materials such as garnets, ferrites and Co/Pt multilayers are briefly discussed.

Jan 1, 1992

By M. Huang

A conductivity-based sensor for on-line measurement of free acid was recently built. This sensor is suitable for high ionic strength solutions and its corrosion-free operation is based on induction currents. It has been tested against literature data and measurements made using a previous developed contact-type conductivity cell, with an average difference within 1%. The electrical conductivities of H2SO4?H2O, H2SO4?MgSO4?H2O and NaCl?Laterite-H2Osolutions at temperatures up to 250 °C were discussed. It was found that the solution conductivity depends on various factors, such as the electrolyte concentrations, the type of electrolytes, temperature and the amount of dispersions. A semi-empirical model was developed to account for all the factors discussed. This model was further tested on actual process solutions from the hydrometallurgy of nickel where sulphuric acid solutions containing a variety of metal sulphates and solids. The average difference between the estimated acid concentration from this model and the one from titration was generally less than 5%, which is excellent for industrial applications.

Jan 1, 2006

By A. V. Tarasov

The high efficiency of autoclave processes is attributed to the fact that they are suitable for processing of refractory raw materials, have low capital costs and high productivity, ensure integrated utilization of the feed materials, produce innovative saleable products, completely eliminate any air emissions, provide low-waste or waste-less technology, as well as mechanization and automation of production processes. In the immediate future, it might be expected that autoclave processes will find use on commercial scale for production of heavy non-ferrous metals in combination with other processes (hydrometallurgical, upgrading, sorption and solvent extraction, electrolytic, etc.) to ensure: -Integrated processing of refractory ores and concentrates (pyrrhotite, zinc, copper-zinc, lead-zinc, nickel-cobalt, copper, pyrite); -Production of metallic powders of base metals as commercial products (copper, cobalt, nickel, etc.), composites on their bases, final products and saleable salts. Processing technologies incorporating autoclave processes, especially, at the stage of liberation (chemical upgrading) of minerals, are characterized generally by high overall recoveries of valuable constituents significantly exceeding recoveries common for conventional pyrometallurgical processes (for some elements by several tens of percent). An example is processing of low-grade refractory pyrrhotite concentrates using autoclave liberation of feed material under pressure of a new reagent, i.e., sulfur dioxide. The use of sulfur dioxide ensures a significant improvement in the recoveries of non-ferrous metals and platinoids to sulfide concentrate and smelting of the latter increases the capacity of the smelting units employed and minimizes the yield of discard slag and loss of metals in slag; in addition, it resolves the problem of sulfur dioxide utilization.

Jan 1, 2003