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By Gökhan Demirci, Ishak Karakaya

"Energy consumption in electrolytic magnesium cells is well above the theoretical values. However, the mechanism of the back reaction, the main cause of the current losses, has not been fully understood yet. Magnesium dissolution into the melt is generally regarded as the limiting step for the back reaction. Accordingly, present cell designs are made with priority given to fast magnesium removal from the cell. However, experimental data and modeling results in this study indicate that the limiting step for the back reaction between magnesium and chlorine is the chlorine dissolution into the electrolyte when physical contact between electrolysis products was eliminated. Effects of chlorine bubbles on the current efficiency and the cell potential were investigated. Results show that the extent of back reaction is proportional to the chlorine surface area in contact with the electrolyte per unit time, and the cell potential increases with the amount of chlorine bubbles inside the electrolyte.1. IntroductionMagnesium is less dense than the electrolyte in electrolytic magnesium production. Therefore, both electrode products, magnesium and the chlorine gas, move upwards inside the molten salt electrolyte during electrolysis. The upward motion of electrode products promotes the most important current loss mechanism, the ""back reaction"". Separation of the highly reactive species; liquid magnesium and the chlorine gas in the cell, to prevent their recombination is one of the main concerns in cell designs. The employment of large inter-electrode distance or a separation wall in early cell designs; decreased the extent of recombination, but increased the cell voltage and energy consumption. Recent cell designs, on the other hand, make use of lifting action of chlorine gas [1,2] by utilizing smaller inter electrode distances to separate the magnesium and chlorine gas faster. Although energy consumption was reduced, but more physical interactions between electrode products make electrolytic magnesium cells still highly inefficient when energy consumptions are compared with the theoretical values. Today, the most efficient industrial cells utilizing high purity feed operate at 10.5-11.5 kWh kg-1 Mg [3-5] and it is considerably higher than the theoretically attainable value of about 6.0 kWh kg-1 [6]. This large gap demonstrates the necessity of more research on physics and chemistry of magnesium cell electrolysis."

Jan 1, 2011

By M. R. Barkhudarov

Semi-solid metal can be formed into useful products of near net shape and high quality. Use of this method has been limited, however, because of the difficulty of working with metal in the semi-solid state, which has strong shear rate, temperature and time-dependent properties. In this paper we describe a thixotropic model and apply it to the problem of small metal droplets impacting on a flat plate.

Jan 1, 1997

By S. J. Gerdemann

The U.S. Bureau of Mines is studying the kinetics of wet oxidation of sphalerite concen- trate (ZnS) as a possible process for a gravity-pressurized reactor (GPR). At tempera- tures in excess of 200' C, a sphalerite water slurry will react with 0, to form zinc sul- fate (ZnSO,). However, the pressure required to keep the water from boiling at these temperatures has kept this reaction from becoming a viable continuous process. The GPR can easily obtain the high pressures required for this reaction. The reaction rate is complicated by the solubility of 0, in water and the further oxidation of ZnSO, to insoluble zinc oxysulfate (Zn4(OH),S04.4H20). The effects of pressure, temperature, and particle size on the rate of reaction were investigated. Reaction rate was found to be limited by the amount of oxygen in solution. However, at 250" C and 1500 psia, over 90 pct of the zinc was solubilized in less than an hour. The conditions for maxi- mizing the Zn++ in solution, while minimizing oxysulfate formation, are discussed.

Jan 1, 1993

By Larry G. Twidwell, Jannette L. Chorney, Bryce D. Ruffier, Katelyn M. Lyons, Daniel W. Gaede, Ryan J. Foy, Jerome P. Downey

The Metallurgical and Materials Engineering Department at Montana Tech is investigating various methods of extracting and refining rare earth elements from mineral ores and concentrates. As part of this research, an elevated temperature “roasting” process has been evaluated as a means of converting the rare earth elements contained in various matrices to bromides as a pretreatment step in preparation for downstream rare earth element extraction and recovery operations. Laboratory and bench-scale experiments have been performed to assess the effects of varying temperature (150 to 400° C), time (1 to 4 h), and the ammonium bromide to rare earth oxide molar ratio (6 to 24) in the roaster charge. The results show that nearly complete bromination of the rare earth oxide is achievable when the roast is performed under optimum conditions.

Jan 1, 2015

By F. J. Tavera

The colloid flotation of lead carbonate precipitates in aqueous media is studied at a pH of 7. The flotation system consisted of five spargered flotation cells in a serial array. The flotation system was operated under controlled conditions of superficial air velocity, superficial liquid velocity, frother concentration, and collector concentration. The measured variables were gas hold-up, bubble size, superficial bubble surface flux, and lead recovery (reported to the concentrate). The experimental data show that it is possible to separate as much as 97% (w/w) lead from the aqueous media when the superficial gas velocity is 1 cm/s and the superficial liquid velocity is 0.19 cm/s.

Jan 1, 2006

By M. A. Barakat

Large amounts of zinc ash and flue dust containing more than 80 % zinc are accumulated during galvanization processes at the surface of molten zinc bath and in the chimney respectively. Pyrometallurgical recovery of zinc from both of the ash and dust samples has been carried out. The ash was sieved with the help of an industrial sieve shaker provided with mesh sieve having a pore size 0.9 mm. The oversize fraction cut (+ 0.9 mm) was melted at 550 °C under ambient conditions. The produced ingot (1) was analyzed whereas the coarse fraction of the produced slag (+ 0.9 mm) was treated as the coarse ash or added to it. The dust was enriched with suitable fluxing salt prior to heat treatment at 600 °C for 1 h. The produced ingot (2) was analyzed whereas the resulting slag was mixed with the fines of the ash and treated by hydrometallurgical processing to prepare valuable salts of zinc. Parameters affecting recovery processes such as time, temperature and flux percentage were studied. Results obtained revealed that the two prepared ingots (1&2) were successfully recovered with recovery efficiency amounts to =85 %. The obtained samples meet the standard specifications with relatively low price. Also in the light of the strict environmental regulations of pollution control, reuse of these wastes materials will help in keeping the environment clean.

Jan 1, 2000

By F. Nava-Alonso, O. Alonso-González, A. Uribe-Salas, R. Pérez-Garibay

"Cyanidation is the most used method to recover gold and silver from their ores. In this process, other metals besides gold and silver may sometimes dissolve and interfere with the efficiency of extraction. Copper is one of those metals, reaching concentrations as high as 1000 mg/L in some cyanidation plants, making difficult the extraction and purification processes, and increasing the operating costs.This preliminary work was intended to study the feasibility of using amines to form a precipitate and to eliminate copper from a synthetic solution containing high copper and cyanide concentrations, as is the case of some cyanidation effluents. The solid formed is removed from the solution using conventional filtration techniques. Seven amines were evaluated at different pH values and amine additions. Up to 90% of copper present may be removed at the natural pH of the effluent (alkaline). The remaining copper would permit to recycle the solution back to the cyanidation process. IntroductionCopper is generally considered the most problematic metal in gold leaching due to the rapid formation of copper cyanide complexes when some readily-soluble minerals are processed (e.g., azurite, malaquite, cuprite, chalcocite and bornite). The copper solubilization as cuprous cyanide complexes leads to a significant economic penalty in terms of excessive cyanide consumption and high cost for cyanide elimination. When activated carbon is used to recover gold and silver, the copper-cyanide complexes decrease the efficiency of the process because of the competition of the cuprocyanides with the aurocyanide for the adsorptive sites on the activated carbon (Rees and Deventer, 1999).Several techniques have been developed to attempt to overcome the problems caused by the copper presence in cyanidation solutions, notably: acidification-volatilization-regeneration (AVR), ion exchange-electrolysis or solvent extraction-electrowinning (Lu et al., 2002). In this work the use of some amines is proposed to remove the copper-cyanide complexes by precipitation of a copper-cyanide-amine solid. The process was evaluated for different amine additions and pH values, using copper-cyanide synthetic solutions of composition similar to that presented by some cyanidation plants with high copper."

Jan 1, 2008

By P. Mazumder

Numerical analysis is carried out to examine the effects of thermosolutal convection on the formation of complex patterns in directionally solidified binary alloys. A finite-difference analysis is used for dynamic modeling of a two-dimensional prototype of Vertical Bridgman system that takes into account heat transfer in the melt, crystal, and the ampoule; melt flow and solute transport. Actual temperature data from experimental measurements are used for accurately describing the thermal boundary conditions. A range of complex dynamical behavior is predicted in the melt flow due to flow transitions and this is found to be directly related to the spatial patterns observed experimentally in the solidified alloys. The model is applied to single phase solidification in the Al-Cu and Pb-Sn systems to characterize the effect of convection on the macroscopic shape of the interface. The application of the model to hyper-peritectic alloys in the Sn-Cd system shows that the presence of oscillating flow can give rise to a novel convection induced microstructure in which a tree-like primary phase in the center of the sample is embedded in the surrounding peritectic matrix.

Jan 1, 1999

By G. Scavino

A 0.5 wt.% C, 22 wt.% Mn austenitic steel, recently proposed for fabricating automotive body structures by cold sheet forming, due to favorable overall strength and ductility, exhibits plastic localizations during uniaxial tensile tests, whereas no localization happens during biaxial Erichsen cupping tests. Full-thickness tensile and Erichsen specimens, cut from as-produced sheets, were polished and tested at different strain rates. During the tensile tests, the plastic localization phenomena consist first of macroscopic deformation bands traveling along the tensile axis, and then of series of stationary deformation bands, each adjacent to the preceding ones; both types of bands involve the full specimen width and yield macroscopically observable surface relief. No comparable surface relief was observed during the standard Erichsen tests. The stress state being known to influence plastic localization phenomena, reduced-width Erichsen tests were performed with 10 to 30 mm width polished specimens, in order to explore the transition from biaxial to uniaxial loading.

Jan 1, 2009

By Zhuo Sheng

We have designed a high-temperature Raman micro-furnace and cell that is suited for the electrochemical process study of the NO3 − in molten NaNO3– KNO3 (fraction of NaNO3 50 wt%) salt. During the cycle voltammetry and constant potential electrolysis process, the Raman laser beam was focused near the electrode; subsequently, the Raman spectra are obtained and the reduction process of NO3 − is analyzed. In the CV cathodic scan process, the new peak attributed to the ν1 mode of NO2 − emerges, and the peaks assigned to superoxide ions (O2 −) and peroxide ions (O2 2−) are not found. In the constant electrolysis process, the peaks at 1130 and 800 cm−1 appear when the potentials are between −2.0 V and −3.2 V (vs. Pt). The results show that when the NO3 − is reduced in molten the NaNO3–KNO3 mixtures, the reduction product O2− cannot stably exist, and O2− will react with NO3 − to form of superoxide ions (O2 −) and peroxide ions (O2 2−).

By B. K. Chakrabarti

Modeling and a screening design of experiment (DOE) was performed with the process variables to identify the greatest effect of variables on the response quality in the dead burning of magnesite refractory in a rotary kiln. Among various interdependent variable factors, the design variables chosen were raw magnesite (RM) feed rate, kiln rotation time i,e, seconds per rotation(SPM) and burning zone temperature (BZT). The response variables chosen were exit gas temperature and density of dead burnt magnesite(DBM). ANOVA and normal plots were used to evaluate the effects.This work had enabled to correlate the BZT, RPM, RM feed with the exit gas temp and density of magnesite produced. The result opens up an avenue to look into the optimum region of operations within the ranges of variables considered in order to conserve energy and to minimize the exhaust gas temperature and to maximize the density of the DBM produced

Jan 1, 2015

By N. Menad

The formation of the dioxins can be dependent on the quantities of carbon, hydrogen, chlorine and oxygen present in a given system, as well as on parameters such as temperature and pressure. Inadequate supply of combustion air ( incomplete oxidation ), low combustion temperatures ( incomplete combustion ), and insufficient turbulence in the combustion are factors which can favour their formation. Dioxins were produced also calatytically from chlorinated phenol precursors, non-chlorinated compounds that were chemically, and reaction of phenol with inorganic chloride. In this paper different precursors such as combination of C, H, 0, Cl, rapid formation/combustion intermediates and routes to PCDFs are reviewed, and the influence of PVC amount on the formation of these isomers is discussed.

Jan 1, 2000

By Maura Malone, Neil Gao, Daniel Liu

"Corrosion is the primary failure mode for aluminum cathode sheets used in Teck's Trail Operations electrolytic zinc plant. It was observed that the corrosion performance of Al cathodes from different suppliers varied considerably. This suggests that the material properties of Al cathodes have a strong influence on corrosion resistance. In the current study, various types of Al alloys, including 1050, 1060, 1070, HIS and 1090, were characterized through chemical analysis, corrosion testing, mechanical testing and metallography. The results are discussed with a focus on the effects of impurity elements and second phase particles on corrosion resistance. The findings were used to improve the Al cathode sheet specification and to develop a standardized screening procedure which details qualification steps for comprehensive evaluation prior to a plant trial.IntroductionAluminum (Al) cathode replacement is a major operating expense at Teck's Trail Operations zinc electrolytic plant. Currently, approximately 0.5% of daily stripped Al cathodes are removed from service because of failures caused mainly by corrosion. Edge corrosion and acid (solution) line corrosion are the most severe types of corrosion, resulting in more than 50% of cathode failures.Corrosion of Al cathodes has been intensively investigated for over two decades and the origins and mechanisms of Al cathode corrosion are well understood [1-4]. Halide anions contained in the electrolyte are the primary culprits for the corrosion and sticking problems of Al cathodes. Both fluoride (F') and chloride (Cl"") result in localized passivity breakdown on the surface of the Al cathode, causing pitting corrosion. Bouarzaiga investigated the corrosion of Al cathode samples partially immersed in electrolyte and found that the formation of Ch at the electrolyte/air interface was the primary contributor to solution line corrosion [2]. Because of the significant impact of F"" and Cl"" on Al cathode corrosion, it is imperative to maintain these concentrations as low as possible in the electrolyte."

Jan 1, 2012

By Hideyuki Itou

Municipal wastes are mainly incinerated in Japan. Both bottom ash and fly ash from the incineration treatment are smelted recently to decrease the volume. Direct smelting of municipal wastes is also becoming popular. The smelting treatment generates fly ash which contains concentrated heavy metals such as Zn, Pb and Cu, and the harmfulness is causing concern. The smelter fly ash is mainly landfilled after stabilization. An effective treatment process of the smelter fly ash is required to recover the metals. For the treatment process, an application of chloridizing volatilization technique is considered. Chloridizing volatilization experiments were carried out to determine the effects of various factors on the volatilization behaviors in this study. A pretreated ash was mixed with a main raw material which mainly consists of hematite. Calcium chloride water solution was added into the mixture. The mixture was pelletized, dried and used as samples for the volatilization experiments. The sample was placed in the reaction tube heated in an electric resistance furnace. 5%02-95%N2 gas with controlled humidity was introduced into the reaction tube. Effects of humidity in the carrier gas, addition of calcium chloride and mixed ratio of the ash to the main raw material were investigated on the volatilization of Zn, Cu and Pb. To determine the volatilization behavior, samples were taken from the furnace at specified temperatures on the heating stage. In addition, experiments at specified holding temperatures for 15 minutes with shortened heating time were conducted. The two series of experiments revealed the effect of heating temperature on the volatilization behavior of Zn, Cu, Pb and Cl.

Jan 1, 2006

By N. Gopalakrishnana, R. Beccard, S. Lourdudoss, R. Holz, M. Deschler

"Rapid growth of conducting and/or insulating InP, GaAs, Gao.47In0.53As, and GaAs0.6Po.4 on one or more of (001), (110), (111)A, (3ll)A and (3ll)B surfaces by Hydride Vapour Phase Epitaxy (HYPE) is demonstrated. The maximum growth rate of the binaries lies between 12 and 300 µm/hr and of the ternaries between 7 and 170 µm/hr. A simple model is developed to describe the influence of crystallographic orientation on temperature dependent growth rates. The growth rates predicted by the model is compared with the experimental values. Room temperature resistivity of insulating InP:Fe can be as high as 5xl09 ohm cm. Temperature dependent differential resistivity is also analysed. This feasibility of growing conducting and insulating layers rapidly on different orientations is very useful for electronic and optoelectronic devices.IntroductionRecently there is a renewed demand for very thick layers of III-V compound semiconductors for high performance electronic and optoelectronic devices [1]-[2]. Long wavelength high speed lasers that can be modulated up to 30 GHz necessitate epitaxial growth of semi-insulating (SI) layers [3]. There is also an increased interest on the growth of epitaxial layers on surfaces other than (001) surface. Epitaxial growth of these materials on such surfaces is of theoretical importance besides being technologically relevant. These demands led us to focus on the growth of conducting and insulating III-V compounds by Hydride Vapour Phase Epitaxy (HYPE). lnP, GaAs, Gao.471no.s3As on lnP and GaAso.6Po.4 on GaAs were grown as conducting materials using Low Pressure HYPE (LP-HYPE) on (001) 2° off substrates. Gao511no.49P on (001) GaAs substrate and lnP on lnP substrates of (001), (110), (l 11)A, (31l)A and (3 ll)B orientations were grown as semi-insulating materials using Atmospheric Pressure HYPE (AP-HYPE). In this report we present the growth aspects of these materials. We also present a simple model on the growth of InP on substrates of various orientations. The theoretically obtained temperature dependent growth rates are compared with the experimental values. Differential resistivities of semi-insulating lnP grown on substrates of various orientations as a function of temperature are also summarised."

Jan 1, 1998

By Jian Li, S. Penttilä, P. Liu, W. Zheng, C. Bibby

"The materials selection for Gen IV supercritical water reactor in-core components faces major challenges due to severe operating condition. The current Canadian pressure-tube supercritical water (SCW) concept design requires core outlet temperature of 650 °C at 25 MPa with peak cladding temperature reaching as high as 850 °C. Aside from oilier challenges, there is currently very limited data on candidate stainless steels' corrosion resistance under this operating condition. Austenite stainless steels that include 316L, 304H, AL6XN and 3 l0S that cover a wide range of Cr contents are promising candidates for either direct in core applications or as base coating materials. However, their corrosion resistance has not been tested systematically under this stringent condition. In this study, these types of stainless steels are tested, and their corrosion resistances are compared.IntroductionThe Canadian pressure-tube supercritical water (SCW) concept will operate at a core outlet temperature of 650 °C at a pressure of 25 MPa, with potential peak cladding temperature reaching as high as 850 °C. High-temperature corrosion resistance is one of the key design requirements for fuel cladding components. As summarized by Allen [1 ], most testing to date has been carried out at temperatures below 730 °C. To date, SCW corrosion data above 600 °C is very limited. Even at relatively low temperature exposure to SCW (e.g. 500 °C), F/M steels develop a thick oxide layer rapidly, while some austenitic stainless steels develop thinner surface oxide. Ni based alloys appear to form very thin surface oxide, however pitting was observed in the vicinity of intermetallic precipitates [2-5]. Dissolution of major alloying components from all of these alloys could also pose significant problems for downstream piping [6]. Kaneda et al. [7] suggested some modified stainless steels provide better SCW general corrosion resistance, with no sign of SCC under the slow-strain rate test.Cho [8] suggested that as the Cr content increase, general corrosion resistance improved at 510 °C and 25 MPa. However, similar to Cho's work, most of the SCW corrosion resistance assessments were based on weight change measurement. This can be unreliable due to potential exfoliation of thick oxide film. Besides, there have been no systematic SCW corrosion resistance tests for candidate stainless steels under higher temperatures. SCW corrosion rate increase dramatically for alloys tested at 600 °C [1]. It is also important to understand the role of major alloying elements under this stringent operating condition, not only for fuel cladding components' materials selection, but also for coating materials development."

Jan 1, 2013

By Hannu Johto

Boliden Harjavalta has operated a flash smelter for nickel sulphide concentrates in Finland since late 1959. The original nickel flash smelting process was modified in 1995 to a novel nickel matte smelting (DON) with semi-low iron where the batchwise operated converting became obsolete. Since that, the process has been applied to multiple chemically variable nickel sulphide concentrates with high environmental performance. In this paper, the status of the current smelter operations is described together with the recent modernizations of the nickel flash smelting furnace and the slag cleaning furnaces.

By G. Van Weert

The pellet reactor was developed approximately 20 years ago in the Netherlands for softening drinking water. Since then, some 35 plants have been built, ranging in capacity up to 8500 m3/h. Applications now also include removal of phosphates and fluorides and the production of metal carbonates and sulphides from waste streams. The pellet reactor consists of a fluidized bed, wherein the process solution is thoroughly mixed with the precipitation reagent at special inlet nozzles to give over-saturation of the compound to be precipitated. In water softening applications, the compound is CaCO,. In the case of nickel or other metal waste streams, Na2CO3 solution is added in sufficient amounts to precipitate metal (hydroxy) carbonate on the fluid bed particles. These grow typically to dense spheroids, which are removed when they reach 0.8 to 1.0 mm diameter. These spheroids are easily dewatered, free flowing and low dusting. The latter property is becoming an attractive advantage in connection with new plant hygiene regulations. The operation of a 60 cm diameter pellet reactor on nickel containing plating waste is described and the properties of the produced nickel carbonate spheroids are discussed.

Jan 1, 1993

By Mamoru Kuwabara

A high-power sound which can transmit through any continuous elastic medium with less attenuation, particularly in liquid allows us to externally control the system of concern by using the acoustic radiation force or the cavitation phenomena. These functions may eliminate gravitational and/or atmospheric constraints which are often encountered in conventional operations for producing clean and advanced materials. This paper outlines the recent development in the field of sonoprocessing of materials. Cold model experiments in some vessels have been performed to simulate ultrasonic operations such as inclusion removal from liquid, degassing of melt, emulsification of two liquid phases, solidification processing, and decomposition of chemical species in waste water. High speed visual imaging is carried out for better understanding of the cavitation phenomena as well as the followed microjets during the processing. The radiation force acting on fine suspending objects in a fluid can be utilized for eliminating or rearranging/orienting the objects in the fluid. Acoustically induced cavitation phenomena in liquid can be utilized as an effective dynamic means to control interfacial phenomena as well as micro- and macro-mixing of liquid. Sonochemical and thermal effects in cavitation multi-bubble can be also useful in a waste water treatment.

Jan 1, 2006

By C. Lupi

The electrorefining of primary copper is a well known technology: in this work copper scrap was directly processed in the same way. he copper and copper alloy scrap was previously pressed by means of a 20 tons apparatus in order to avoid pyrometallurgical operations. The samples obtained in this manner showed a good compactness so that they were used as anodes in the electrorefining tests. The tests were carried out on anodes made by copper scrap, copper alloy scrap and a mixture of the two. The electrorefining tests were performed at both 303 and 333 K, in a perspex cell having a volume of 500 ml using a current density of 250 A/m2. The cathode used was always a sheet of pure copper and the electrolyte composition was 40-50 g/l Cu as CuS04 and 150-200 g/l H2SO4. Current efficiency in the range of 92-97% and specific energy consumption ranging from 0.14- 0.20 kWg of copper were reached in all the tests. The refined copper deposits were analyzed by AAS to verify their purity and observed by SEM to highlight their morphology.

Jan 1, 1998