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By A. G. Raraz

Reactive metal electrorefining presents a number of problems that pose obstacles to commercial operation. Cerium has been chosen as the surrogate for certain reactive metals because of its thermodynamic and electrochemical characteristics. A comparative review of the properties for cerium and plutonium has been presented to justify the choice of cerium as the surrogate metal for studying electrorefining. This review has addressed the electrochemical, thermodynamic, and kinetic parameters of molten salt electrorefining of cerium metal to provide an insight to this extremely important process. The cell components and configuration, current efficiency of the process, purity of the cathodically deposited metal and the power requirement of the system are evaluated for a molten CaCl2-MgCl2 salt electrolyte using a molten, stirred impure anode. Crucible designs, salt electrolyte, cell temperature and electrode materials are also evaluated. Selection of the salt electrolyte and the cell temperature have been suggested from this study.

Jan 1, 1992

By Y. Z. Zhang

Electrochemical oxidation of arsenopyrite in ferric sulphate media in the absence and presence of bacteria T jerrooxidans has been investigated for the purpose of understanding the dissolution chemistry of arsenopyrite and the bacteria attack mechanism. Mixed potential, polarization resistance measurements, polarization curve, cyclic voltammetry experiments were conducted in a ferric sulphate medium of 10g/L FeH, temp.25-35°C, pH 1.5-2.5 in the absence and presence of bacteria Tjerrooxidans, respectively. For the anodic process, a two-step reaction sequence is suggested by the electrochemical measurements. The initial step at a low potential is described by:

Jan 1, 1996

By E. J. Peterson

Oil shale retorting induces mineral and chemical reactions to occur on the macroscopic and microscopic levels in the kerogen-bearing marlstone. The nature and extent of the reactions is dependent upon process variables such as maximum temperature, time at temperature, atmosphere, and raw shale composition. This report describes the investigation of the mineral, chemical, and trace element release properties of spent shales retrieved from an experimental in situ retort at Occidental Oil Shale, Inc. 's Logan Wash site in Garfield County, Colorado. Correlation between mineralogy of the spent materials and the mobility of major, minor, and trace elements are indicated, and relationships with important process parameters are discussed. The progress .of carbonate decomposition reactions and silicat ion reactions is indicative of the processing conditions experienced by the shale materials and influences the mobility of major, minor, and trace elements when the solids are contacted by water. Shale minerals that are exposed to the extreme conditions reached in underground retorting form high temperature product phases including akermanite-gehlenite and diopside-augite solid solutions, kalsilite, monticellite, and forsterite. The persistence of relatively thermally stable phases, such as quartz, orthoclase, and albite provide insight into the extremes of processing conditions experienced by the spent shales. Leachate compositions suggest that several trace elements, including vanadium, boron, fluoride, and arsenic are not rendered immobile by the formation of the high-temperature silicate produce phase akermanite-gehlenite.

Jan 1, 1981

By Jiang Fan, Liu Shi, Wang Haigang

Winter-time natural convection in gravel embankments has been suggested as a technique to provide passive cooling and thereby avoid thaw-settlement of roadways located in permafrost areas. Numerical simulation by finite volume method on the proposed model is perf9rmed using the software FLUENT. A gravels model, in which the embankment is composed of stones and air, has been adopted to investigate the temperature and velocity fields in embankment. Simulation results show that in summer, a weak clockwise circulation of the pore air extending throughout most of the embankment. The pore-air motion is very weak which results in relatively straight horizontal isotherm lines. And heat transfer is mainly maintained through conduction. But in winter, pore-air velocities are higher and multiple vortexes are formed in the embankment. Natural convection then becomes the dominant influence on the isotherm shapes within the embankment. As a result of low ambient temperatures exerted on the embankment surface during winter months, an unstable air density gradient develops within the embankment. This convection increases the heat flux out of the embankment. Therefore, the winter-time convection can further reduce the temperature of the foundation soil beneath the open-graded embankment. In addition, the effects of the size of the stones within the embankment have been analyzed and compared in the gravel model. It shows that in winter, 200mm stones lead to stronger vortexes in the embankment compared with those of 60mm stones. Consequently, the zone oflow-temperature beneath the embankment is extended.

Jan 1, 2004

By Cody Burcher-Jones

The recovery of rare earth elements (REEs) through heap leach/in situ techniques from so-called ion adsorption clays (IACs) is attractive due to their inherent simplicity. However, the underlying mechanisms of these processes are poorly understood. In this study, the deportment of REEs in a typical IAC material has been investigated and was found to concentrate in the phyllo-layers of the clays, especially hallyosite, and was readily desorbed by various ion-exchange reagents indicating various potential routes to liberate them. Here we are reporting the use of seawater (0.5 M NaCl), spiked with various amounts of (NH4)2SO4, and found better extraction using a reagent mixture than NaCl on its own. Further, the leaching of REEs from a bed of clay material was investigated over time to understand the rate of transport through the stagnant material. Results indicate that REE release is likely to be controlled by diffusion through the clay material, while desorption in agitated systems is rapid. A degree of fractionation between different REEs can be observed during diffusion. Nonetheless, the successful operation of in situ leach operations for this type of material would depend primarily on how easily solution cocktails can be made to flow through the bed material.

By Nobuhiro Ishikawa

The in-situ observation of the effect of impurities on the reduction process of iron oxides by C in TEM was carried out. A few wt% of CaO or AbO, was used as impurities in FeO was prepared. Some precipitates grew into the C layer expect for using 3.0wtCa. The reaction between FeO and carbon was much different from using pure FeO at about 800-1 lOOK. The rate of reaction became much slower including Ca and almost no reaction was happened with the concentration of CaO up to 3.0wt%. On the contrary, AbO, had ahuost no effect on the reaction. The results indicated that Ca suppressed the reaction and the effect of Al was much less. The precipitates which grew into C layer accompanied almost no Ca and AI. Only Fe was detected in the precipitates.

Jan 1, 2008

By Ahmet Geveci

In this work it is aimed to assess the plant analytical data which appeared during efforts to decrease the effect of carry-over slag (basic oxygen furnace slag) that can not be prevented to leak during tapping of steel in the ladles. While the amount changes, carry-over slag that escaped to ladle, consists of appreciable amount of reducible oxides (?FetO? and MnO) which act as oxygen source for steel bath. By using aluminum dross, containing %30-35 metallic aluminum, which is a non-recoverable process outcome (discard) for most of the aluminum factories, slag reduction behavior will be analyzed together with other parameters such as reaction time, initial amount of total Fe+MnO, amount of reducing agent and reducing effect of soluble aluminum in steel bath while obtaining a slag composition which promotes higher desulphurization capacity and inclusion removal for liquid steel.

Jan 1, 2006

By Kenneth N. Ham

Hydrometallurgy covers a wide spectrum of areas and its knowledge base is enlarged and enhanced by contributions from many other fields. Dissolution of metals and alloys in aqueous media will be used to illustrate how rich the field of metal extraction can be. Comprehensive understanding of the fundamentals of metal and alloy dissolution in aqueous systems requires creative application of thermodynamic principles, solutions chemistry, ligand complexation theory, electrochemistry, transport phenomena and heterogeneous kinetics. In addition, recent developments in instrumentation in the fields of interfacial phenomena and corrosion have tremendously advanced the field of metal extraction in aqueous system. The close relationship between metal extraction in aqueous systems and various physicochemical phenomena occurring in corrosion and interfacial systems will be discussed and illustrated with examples.

Jan 1, 2002

By Akira Yazawa

To realize highly efficient process in extractive metallurgy, continuous operation nearly in equilibrium is preferable, but most metallurgical processes consist of plural steps with different chemical potentials. Traditional two-step process of sintering followed by reduction is continuous in each step, but is heterogeneous reaction system far from equilibrium, and the chemical potentials are varied considerably along the distance the charge travels in a reactor. This route will become old-fasioned in next century due to the various inherent problems caused especially by sintering process. To establish reasonable new smelting processes, the important tasks of the metallurgists are how to introduce feed and reacting gas in the reactor, and also how to overcome the difference in chemical potential in the reactor system. Based on the ways to solve theses tasks, recent proposals of new smelting process for copper and lead are classified and discussed with the help of sulfur-oxygen potential diagram. On such potential diagram, each equilibrium step in continuous smelting is expressed at a fixed point, and two reactors with different chemical potentials must be connected by continuous molten flow through launder or partition wall. In the latter case, the reactor is apparently single, but some technical problems must be overcome. While, in a batch smelting like converter, potential variation is successively realized along a path on chemical potential diagram with the time elapsed. To establish immediate equilibrium, continuous steady flow of reactants into well mixed reactor is indispensable. In modern smelting process, the ore is mostly supplied in the form of powder which have huge surface area and fluid character, and consequently injection process must be very attractive. Several examples are discussed for both of copper and lead smelting, and promising future technologies are suggested.

Jan 1, 1988

By P. T. Velu, R. G. Reddy

"The use of emf measurements to derive classical thermochemical data has been in use for many years. The reaction associated with electrochemical process is harnessed in a galvanic cell and energy involved measured in terms of electromotive force. The property requirements of sensor electrodes used differ for various aqueous, molten salt and solid electrolyte systems. The electrodes for molten salt electrolytes need special care for construction. This paper describes the studies carried out using an Ag/ AgCI reference electrode. This electrode was used to measure the solubility of compounds in molten salt electrolytes. The results obtained using this electrode are in excellent agreement with the values from chemical analysis method.I. IntroductionThe technique of obtaining a metal from its oxides by electrolysis is more than a century old process now. In these processes, it has been well established that for halide electrolytes, only the dissolved oxides are available for the dissociation at the electrode to release the metal during electrolysis. Therefore, the solubility of metallic oxides in the molten salt electrolytes is an important parameter which determines the economical and technical viability of these processes. The widely used molten salts systems in halides are fluorides and chlorides. The fluoride electrolyte system is used in our present study.The viability of obtaining aluminum alloys by in-situ electrochemical processing has been outlined in our earlier publications[1-8]. Studies on the solubility of various alloying element compounds is a part of our ongoing research efforts for the direct production of Al-Li alloys. As mentioned above, the solubility of lithium oxide and lithium carbonate compounds in molten fluoride electrolyte system have studied using EMF technique. The change in potential of the molten electrolyte was measured by a working electrode against the reference electrode with the addition of lithium compound."

Jan 1, 1997

By Ryokichi Shimpo, Akio Fuwa

"The process-measurements of copper smelters in Japan were investigated for the summary of the latest technique and for the fundamental study of process control. The smelters investigated are those employing flash smelting furnace and P.S. converter, one reverberatory furnace and P.S. converter, and one continuous smelting converting furnace (M.I. process). Respective process is then considered, consisted of several reactors of different functions. The measurement methods were summarized in each reactor, including the measurement points. The methods of chemical analyses of the samples in each reactor were also investigated.IntroductionAn investigation on the process measurements, chemical analyses, and system control in copper smelters in Japan were carried out for understanding and summarizing the technique of the pyrometallurgical copper smelting operations. The typical seven processes in six copper smelters were investigated in the period from 1985 to 1987. The smelters investigated were Touyo Smelter of Sumitomo Metal Mining Co., Ltd., Kosaka Smelter of Dowa Mining Co., Ltd., Saganoseki Smelter of Nippon Mining Co., Ltd., Tamano Smelter of Hibi Kyodo Smelting Co., Ltd., Ashio Smelter of Furukawa Co., Ltd. and Naoshima Smelter of Mitsubishi Metal Co., Ltd. They include five flash smelting furnace and P.S. converter systems, one Mitsubishi continuous smelting and converting process (M.I. process), and one reverberatory furnace and P.S. converter system.The investigation was performed by making inquiries about the measurements, chemical analyses, system control, and their future prospects to the engineers in each smelter and by summarizing up in each item. The system control and future prospects were summarized in another paper titled ""Process Control Scheme of Copper Smelting Processes in Japan and Future View."

Jan 1, 1989

By Shinya Otsuka

Activity coefficient of oxygen in sulfide-rich and metal-rich melts in copper-sulfur binary were determined at 1423 and 1523 K by means of a modified coulometric titration technique using the following cell: 0 ( is Cu-S melts) I Zr02 (+Ca0) I air, Pt The activity coefficient values obtained in the present study increase rapidly with sulfur composition in the vicinity of xs = 0.3333. The data obtained for the matte saturated with the metal-rich melts are in good agreement with those obtained by Kuxmann and Benecke, Schmied 1, and Eguchi and Yazawa. Those obtained for the metal-rich melts are in good agreement with the results of Sano and Sakao.

Jan 1, 1983

By Vianey Garcia-Osorio

One of the problems in the carbothermic aluminum process is the substantial loss of aluminum compounds as vapors due to the high temperatures in the process. In order to solve this problem a Vapor Recovery Unit (VRU) is proposed. In this unit operation the aluminum vapor undergoes a series of heterogeneous non-catalytic reactions forming solid, liquid and gas products. In this work a model for the simulation of this unit was developed which includes heat and material balances as well as heterogeneous non-catalytic reactions. The model leads to a system of differential equations; its solution was implemented in Matlab giving as a result a stage-by- stage solid-fluid reaction model.

Jan 1, 2001

By J. Smuts

The mixed-valence iron silicate ISCORITE (Fe7Si010) was identified recently in a number of ironmakingmater1als, some of which were first produced more than a century ago. Although the existence of iscorite was not reported before 1967 and published phase diagrams do not make provision for it, the morphology of the phase in all the materials that were examined suggests that it is stable under a variety of conditions. It is shown that is-corite can accommodate various foreign cations in its lattice where they can replace Fe and/or Si. The morphology of is-corite in a number of materials of different origin is shown in relation to iron oxides and silicates in optical and SEM/BSE images.

Jan 1, 1991

By Ahmet Geveci

[Generally accepted formula related to sulfur slag-metal distribution ratio is given by the following equation: [ ] According to the above equation it can be deduced that sulfur distribution between slag and metal is governed mainly by metal composition (?s term), slag composition (slag basicity and in turn sulfide capacity), oxygen potential of the system (ao¬¬ term) and temperature(related to equilibrium constant, K). In this study, the results of ladle furnace operations conducted in Erdemir-Iron and Steel Works Co. (Turkey) in relation to sulfur removal, have been given. Typical ladle furnace slag analyses of 4937K quality steel have been presented. Activity coefficient of FetO,?FetO, have been calculated with the relation obtained fromthe literature. Activity calculations have been performed with the program written in Mathcad. The changes in activity of aFetO in the slag phase,, have also been studied in relation to the sulfur removal: The relation between % Decrease aFetO and %DeS (measured)have been investigated for 4937K runs and someother types of steel produced in the Erdemir Plant. Related to ladle operations %desulfurization defined as [(%Sinitial-%Sfinal)/S%initial]*100 values have been presented for different steel qualities.]

Jan 1, 2006

By W. G. Davenport

This chapter extends our mathematical description of flash smelting to -nitrogen in the flash furnace blast. As in chapters 4 and 5, the discussion is limited to auto thermal smelting (no hydrocarbon combustion). Hydrocarbon combustion is introduced in Chapter 9. Outokumpu flash furnace blast is a mixture of air and industrial oxygen. Most of its N2 originates in the air portion of the blast. A small portion originates as an impurity in the industrial oxygen. The nitrogen entering a flash furnace must always be heated from its input temperature, 298 K in this chapter, to its off gas temperature, -1500 K. Energy must be supplied for this purpose. With auto thermal smelting, the energy is-provided by oxidizing extra Fe-and S.

Jan 1, 2001

By Eric J. Grimsey

Nickel smelting and converting can be viewed as processes in which iron is either partitioned or transported between matte and slag. Metal recovery depends on the mass of iron transported to slag, the thermodynamic environment in which the transport is made, and the extent to which the slag, once formed, is left in contact with the matte. The importance of these effects is discussed with reference to a new equation which describes metal recovery in terms of a mass balance and a thermodynamically related parameter which is easily measured in practice.

Jan 1, 1993

By Wenjun Duan, Zongliang Zuo, Qingbo Yu, Qin Qin, Junxiang Liu

Moving bed has been widely used in the field of heat and mass transfer and reaction between solid particles and gas. In order to enhance the heat exchange coefficient, there will be tube banks inserted in the moving bed. In the process of drying ammoniates particles or heat recovery from high-temperature particles with moving bed, the particles flow behavior around the tube banks is significant. In this paper, the particles flow behavior around the tube banks is investigated, and all the results can provide guidance for the design and operation of a moving bed.

Jan 1, 2016

By Bruce R. Conard

Consideration of environmental and human health issues in metallurgy is growing rapidly. While not all metallurgists need to have detailed expertise in environmental and health questions, they should be aware of the challenges the metals industry faces, be able to interact with colleagues in other sciences and contribute to sound metal resource management. Hydrometallurgists occupy a unique position among metallurgists because of their knowledge of the behaviour of metals in aqueous systems, which are of fundamental importance in understanding environmental chemistry and human toxicology. As a result, hydrometallurgists should more frequently and passionately lend their expertise in assessing environmental and health risks of metals and in helping to develop effective global guidelines, regulations and process and product stewardship strategies, thereby enabling metals to continue their beneficial service to society.

Jan 1, 2003

By Jinqian Zhao, Jiarong Li, Shizhong Liu

"Creep cavitation of in single crystal (SX) superalloy was investigated. The constant load creep tests, in single crystal superalloys DD6, were conducted at the conditions of 800°C/700MPa, 850°C/550MPa and 900°C/450MPa, respectively. It was found that there were square facets on the stress fracture surface, and microscopic cavities in the ruptured specimens in the vicinity of the fracture surface. Both the square facets on the fracture surface and microscopic cavities in the section of the ruptured specimens show the morphology of the same thing at the different views, namely creep cavities, which are take the form of flatten cuboid. In fact, creep cavities are the longitudinally tensiled creep cracks slowly growing during the stress tensiling. The factors of creep cracks nucleation and growth conditions include: (a) enough high temperature to activate diffusion (b) casting pores as nucleation origination (c) high strains and strain rates. Eventually, the instantaneous fracture mechanism of creep specimen is cleavage fracture.IntroductionFor the materials used in elevated temperature service, creep behavior has to be accounted for. It is well recognized that creep rupture in polycrystalline materials at high temperature occurs principally by the nucleation and growth of microscopic cavities at grain boundaries, followed by microscopic cavities linkage to form micro- and eventually macro-intergranular cracks[l,2]. Without the usual grain boundaries, SX superalloys have superior capabilities at high temperatures to polycrystalline superalloys, and have become an established feature of gas turbine technology where they are commonly employed in the manufacture of high performance blades[3]. A considerable amount of work has been done over the past tens of years, and many models for nucleation and growth of creep cavities have been proposed, however, those are mainly for polycrystalline materials.In order to improve creep resistance that single crystal superalloys, in which grain boundaries are removed, have been developed. Because there don't exist grain boundaries in SX superalloy, the mechanism of nucleation and growth of creep cavities must be different from that in polycrystalline materials.Understanding the formation and characteristics of creep cavitation is crucial to model the lives of single crystal superalloys.M. Marchionni and L.G. Zhao et al. found that there were square facets on the stress fracture surface [4,5]. Roger C. Reed pointed out creep cavities lie in the necked region[6]. In this paper, the effects on the formation of creep cavities are discussed, as well as the morphology of creep cavities and fracture mechanism of SX superalloys."

Jan 1, 2013