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By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen temary system, which is of fundamental importance for discussing the recovery of lead and antimony from a used lead-battery, have been investigated at 1173 and 1223 K. The two liquid phases of metal and oxide were observed at the temperatures studied, and the tie lines indicating isoactivities were determined. The activities of PbO, Sb015 and Sb203 in the PbO-SbOu and PbO-Sb203 pseudo-binary systems were then obtained by applying the Gibbs-Duhem equation to the phase relation of metal-oxide equilibrium. Both in the pseudo-binary systems the activities exhibit negative deviations from Raoult's law. The vapor pressures of lead, antimony and lead oxide, antimony oxide were calculated by using the activities of the components in the lead-antimony-oxygen ternary system. As a result, an oxidation of antimony concentrated in an anode slime followed by evaporation as antimony oxide Sb406 was found to be considerably effective for the recovery of lead and antimony from a used lead-battery.

Jan 1, 2003

By Xiaobing Yang, Animesh Jha, Greg Doughty

"Successful use of inert anodes should reduce the CO2 footprint in aluminum production. The search for a “holy grail” inert anode for metal electro-winning from constituent oxides using molten salt bath as an electrolytic medium is continuing. In this article we demonstrate the engineering approaches for the fabrication of intermetallic anodes, based on a quaternary Al-Ti-Cu-M (M:Ni, Fe) system for primary aluminium production. In particular, we examine the microstructural and electrochemical properties of alloys, based on the quaternary compositions. We explain the aspects of phase stability under anodic potential, which leads to the loss of anodic materials in the temperature range of 850-1050oC. The results are analysed in the context of oxidation reaction and formation of oxide layers which readily dissolve in the cryolite melt and prevent passivation. The paper also describes the conditions under which the reduction of aluminium at the graphite cathode occurs which also strongly depends on the molten salt chemistry for the nucleation of molten aluminium at the cathode.1. IntroductionOxygen-evolving inert anodes are an alternative to the conventional consumable carbon anodes for the production of primary aluminium. In this paper the materials selection criteria chosen for the engineering of anode is based on the understanding of the thermodynamic stabilities of aluminide intermetallic phases, some of which are formed and remained stable in fluoride melts. For example, the formation Al3Ti dispersed in aluminium metal via molten-fluoride flux reaction is well known in the context of aluminium casting and grain refining [1-3]. It is for this reason in our research we concentrated on the engineering of stable intermetallic phase mixture in the Al-Ti-Cu ternary system, shown in Figure 1 [4]. In this figure two compositions in the Al3-0.5zTi1-0.5zCuz family are shown with the substitution of 7 atomic % and 11 atomic % copper. However initial investigations showed that these two compositions were unsuitable due to the formation of low-temperature liquid (~540oC) and intermetallic phase, Al2Cu along the Al-Cu binary edge during solidification. The Al2Cu phase segregated along the boundaries of Al3Ti and Al5Ti2Cu, and dissolved away when electrolysis was carried out using these anodes above 800oC. The presence of consequential porosity in the anode material increased the corrosion of the alloy through local heating due to high current density at 0.8 A cm-2. The early tests were carried out with cryolite melts, shown in Figure 2, having 3 weight percent of Al2O3 in the bath at 850oC."

Jan 1, 2010

By Ana E. Bohé, Georgina De Micco, Gastón G. Fouga

"In this work the reaction between several manganese oxides and chlorine is investigated in the range of temperatures between 650 and 950ºC. The reaction path for the chlorination of MnO is established, which involves recrystallization of high valence manganese oxides (Mn3O4 and Mn2O3) followed by its chlorination. For this reason, to understand the reaction of MnO, the chlorination of Mn3O4 and Mn2O3 has also been studied. The starting temperature for the reaction of these oxides is determined by non isothermal thermogravimetric measurements. The effect of temperature is analyzed, under our experimental conditions the rate of reaction is mass transfer controlled. The activation energy for the volatilization of manganese chloride is obtained which is in good agreement with volatilization enthalpy of MnCl2.IntroductionMany oxide ores which have manganese in their composition undergo chlorination processes during the extraction of refractory metals such as Ti, Hf and Nb. Although several works related with chlorination of manganese oxides were reported, there is no information about the kinetics or mechanism of the manganese oxide chlorination reactions. Okahara et al. studied the chlorination of manganese oxides and established that they react easily above 250ºC. Furthermore, they observed that chlorination of high order oxides is more difficult when there is not a reducing agent [1]. Ivashentsev studied the chlorination of manganese oxides using Cl2(g), CO(g) + Cl2(g) and COCl2(g). He established that the reaction of MnO started at 130ºC with formation of MnCl2(s), he also observed recrystallization of manganese sexquioxide [2]. Finally, the chlorination of manganese nodules from the ocean was studied by Murthy and Reddy [3] with the aim of obtaining valuable metals such as Mn, Co, Ni and Cu. They studied the influence of several parameters like temperature, carbon percentage, particle size and chlorine flow rate in the extraction process."

Jan 1, 2008

By C. Zografidis, K. Karalis, E. Devlin, S. Tabouris

"The main parameters affecting energy and electrode consumption in smelting reduction of Greek nickeliferous laterites in submerged arc electric furnaces (E/F) were investigated. Within this framework, the operational data of E/Fs, such as energy consumption indicators, electrode consumption indicators and chemical characteristics of Fe-Ni and slag, were correlated with the physicochemical characteristics of the calcine, produced by roasting reduction of laterite in rotary kilns (R/Ks), such as reduction degree, temperature, chemical composition and granulometry. The results obtained provide a significant input for further research on the modelling of the roasting reduction – smelting reduction process, which is a critical tool for energy optimization.IntroductionThe two main steps of pyrometallurgical treatment of greek nickeliferous laterites for ferronickel production include: i) drying, pre-heating and controlled pre–reduction of laterite ores with solid fuel reducing agents and fuel oil in rotary kilns (R/Ks) for the production of a calcine, and ii) smelting reduction of the calcine in open-bath submerged-arc electric furnaces (E/Fs) for the production of Fe-Ni alloy with 12-16% Ni [1].The energy absorbed from the endothermic reductive reactions of iron, nickel and cobalt oxides (Fe2O3, FeO, NiO and CoO) of the calcine with the remaining carbon in the E/Fs, corresponds to about 16% of the total energy output in the smelting reduction step [1]. This is indicative of the significance of the calcine’s reduction degree for the electric energy requirements in the E/Fs. Moreover, the chemical characteristics and the granulometry of the calcine constitute critical parameters for the energy requirements as well as the smooth operation of the E/Fs."

Jan 1, 2012

By John W. Graydon

Incineration is an attractive alternative to the disposal of MSW in landfill sites. However, the process of incineration generates fly ash which contains significant levels of leachable heavy metals - particularly cadmium, lead, and zinc - and it is essential to manage this fly ash in an environmentally sound manner. The compositions, phases, textures, morphologies and size of fly ash particles have been studied by light microscopy, scanning electron microscopy, X-ray microanalysis, and X-ray diffraction. The detailed spatial relationships and speciation of the environmentally significant constituents have received particular emphasis. The information obtained is useful in understanding how fly ash is formed during incineration, in understanding the leaching behavior of untreated fly ash if it is disposed of in a landfill and, most importantly, in guiding the development of the best treatment strategies for fly asti to mitigate its environmental impact.

Jan 1, 1992

By Jilai Xue, Jun Zhu, Yongqiang Liu

"Up-grading silicon feedstock by removing B and metal impurities can improve process efficiency and lower production cost in metallurgical processing for solar cells production. Hydrometallurgical study has been carried out in laboratory through alternative treatments of the metallurgical grade (MG) silicon (-200 mesh) by using hydrogen peroxide, hydrofluoric acid (4 mol/L) and NH4Cl-NH4 F (30:5) solution. The experiments were usually performed under mechanical agitation at 70 ? for 5 h. ICP-AES analysis showed that B content in MG silicon after the hydrometallurgical treatment has reduced by 92.4 %, and Fe, Al, and Ca contents by 98.8 %, 98.0 % and 81 %, respectively. Kinetics of these processes was also studied for better understanding of the effects of silicon powder size, acid concentration, leaching and oxidizing time on the processing chemistry.IntroductionAs one of the most clean and promising new energy, solar energy is used more and more in many countries all over the world, especially in United States, Japan and European Union. Most of industrialized states have made their national photovoltaic plans, which have stimulated further increase in use of solar energy. Photovoltaic Industry is at a high growth rate about 30 % [1-2]. For silicon solar cells to remain the mainstay for the photovoltaic industry it is necessary to develop a low-cost solar grade silicon feedstock [3]. At the same time, the availability of the currently M-G silicon from the semiconductor industries becomes limited [4]. With the advantages of low cost and low energy consumption, metallurgical routes to product solar–grade silicon get more attention [5]. These routes mainly include pickling, slagging, vacuum processing and directional solidification, etc [6]. Among them the most important processing step is the directional solidification, but it still can not satisfy the industrial demand for removing B. Removing B from Si remains as one of the most difficult and important processes in making M-G silicon [7]."

Jan 1, 2012

By Andreas Siegmund

Cast or rolled lead anodes employed in zinc electrowinning typically contain between 0.5?1.0% silver to decrease the overall corrosion rate. The production of cast lead-silver or lead-silver-calcium anodes often results in the formation of numerous holes, voids or laps in the anode surface that can initiate internal corrosion in localized areas. In rolled anodes the presence of internal porosity is significantly reduced, thus resulting in extended service life. The obtained grain structure of cast or rolled Pb-Ag anodes, however, requires a relatively long period of time to form a stable protective PbO2/MnO2 layer that can evolve oxygen without excessive lead contamination of the cathode. Therefore, these anodes are often mechanically, chemically or electrochemically conditioned prior to being placed in the electrowinning process. RSR Technologies has developed an improved anode for zinc electrowinning. The anode consists of a rolled Pb-Ag-Ca-alloy with controlled surface grain structure. The preferred calcium and silver content of the alloy is 0.05?0.08 % and 0.3?0.4%, respectively. Since May 2001, industrial-scale tests have been carried out at two zinc refineries in North America in industrial electrowinning cells. The controlled grain structure of these anodes allows forming an adherent protective oxide coating within a short period of several days when placed in an electrowinning cell without the necessity of being preconditioned. Anode sludge growth is evenly distributed. The anodes stay dimensionally stable and no short-circuits have been observed. Consequently, low corrosion rates and improved current efficiencies have been achieved.

Jan 1, 2003

By Anupam Madhukar

The essence of an atomistic unified kinetic model of strained thin film growth and defect initiation is presented along with a comparison of its consequences obtained from computer simulations with experiments. Within the competing kinetics of a strain dependent activated incorporation of atoms and an asymmetry between upwards and downwards inter-layer migration, the model provides a consistent description of 2D versus 3D morphology evolution accompanied by the appearance of surface vacancies and steps at no energy cost. The correlated migration of these precursor defects offers an atomistic mechanism for the emergence of surface half-loops from the growth front (thus accounting for configurational and thermal entropy) governed by activation energies closer to their correlated motion under the evolving strain fields and thus substantially less than those calculated with respect to the perfect crystal as the reference state. The essential mechano-chemical nature of the problem is compared and contrasted with the historical literature of such phenomenon as precipitation hardening and sintering in metallic and ceramic composites.

Jan 1, 1994

By D. K. Panda

The behavior of single drops with gas evolution at the interface is of interest because this is one of the important reactions that occur in oxygen steelmaking vessels, where a large amount of iron-carbon drops are dispersed in an oxidizing slag. The carbon dissolved in these drops, reacts with the slag to form CO, which is evolved as a gaseous phase. A room- temperature model was used to study the nature of this type of reaction including the effect of various factors such as viscosity and the presence of surface active impurities. Experiments were done for reacting drops over a wide size range to observe various regimes of behavior. Large single drops were levitated in a counter current flow to produce a sufficiently long residence time to allow the study of the various stages in the reaction. The emphasis of this work was to obtain photographic evidence of a high quality to describe all possible modes of behavior, and so a lot of effort was given to developing and perfecting experimental techniques.

Jan 1, 1994

By Charles A. Sorrell

Two red muds, two fly ashes, and several aluminosilicate minerals were subjected to direct treatment with concentrated H2SO4 at temperatures of 175°C and below. X-ray analysis showed that virtually all the sulfate reaction products remained in the solid residue because of their low solubilities in x SO Substantial portions of the Al2O3 Fe2O3TiO2, Na2O, and K2O components of the materials reacted to form water soluble sulfates, which were then removed by H2O leaching at 55°C. The solid residue after water leaching consisted largely of amorphous silica and, in lime bearing compounds, CaSO4, The reaction and leaching processes were effective in removing all or nearly all the Al2O3. Fe2O3, TiO2, Na2O, and in lime components in the fly ashes, red muds, china clay, bentonites, the nephelioe fraction of nepheline syenite, and a plaster insulating brick composed of anorthite and mullite. Reaction with potassium feldspar and petalite took place, with formation of alkali aluminum sulfates, but the reaction rates and yields were extremely low. Potassium feldspar can be heated with Na2O and x O in air at 700°C for 24 hours, or with CaO at 1000°C for 24 hours, after which the reaction product kaliophilite, nepheline, and leucite-like phases, prove to be very susceptible to H2SO4, reaction and H2O leaching, providing yields near 100% of the Al2O2 content. An alternative method of H SO treatment consists of heating the sample in a silica tube and passing H2SO4 vapor over it. Preliminary results indicate that this method can be effective in enhancing the kinetics of reaction with the Al O component of potassium feldspar and offer the possibility that formation of Al2 (SO ) Fe2(SO4)3 and TiOSO4 can be accomplished selectively by taking advantage of the fact that the upper stability limits of the respective sulfates in the presence of H2SO4 vapor will be different.

Jan 1, 1982

By Fernanda Margarido

Recovery of metals contained in the electrode materials of batteries was studied considering an integrated recycling process constituted by physical and chemical operations. The physical treatment included the shredding of the spent batteries, followed by a wet sieving operation of the fragmented material. The physical behavior of Ni-Cd and Zn-Mn based (alkaline and saline) system batteries was studied and compared. In that sense, shredding operation was performed and the sieving of shredded fractions was accomplished to evaluate the efficiency of the separation of electrodes and scrap. For Ni-Cd batteries the loss of electrode material with the supra fraction (scrap) after the shredding operation was lesser than the Zn-Mn batteries. Especially for saline-type batteries, the electrode attached to the scrap was substantial leading to important losses. This difference can be explained by the composition of the case materials and the internal physical constitution of the electrodes. The wet sieving studies carried out allowed optimizing the separation of the electrode fine fractions from the scrap materials through the analysis of selectivity Cd/Fe or Zn/Fe. For Ni-Cd batteries, maximum selectivity was achieved for the granulometry of 1.4 mm, while for alkaline and saline systems best selectivity were obtained at 2.8 mm and 5.6 mm, respectively. This process allowed the recovery of about 70% of electrodes for Ni-Cd and alkaline systems, and 50% for saline batteries, with less than 5% of scrap as contaminant. This physical step can be considered as a pre-treatment of this type of waste material envisaging its valorization by chemical treatment, as improves the concentration of the elements of interest and decreases the iron content.

Jan 1, 2006

By Peter G. Mason

Over the last 15 years numerous Pressure Oxidation and Pressure Leach plants have been installed throughout the world. The technology is no longer regarded with awe and trepidation as plants designed to treat a wide range of feedstocks continue to be successfully brought on line. Important aspects of the design of such plants include feed preparation, slurry pumping, heating and heat recovery, pressure control and let-down, vessel design, safety and provision of associated services.

Jan 1, 1999

By A. Rios

ENAMl's Paipote Smelter commenced operations in 1951. At present, it processes 230,000 tonnes/year of green feed in a conventional smelter, which comprises one reverberatory furnace, two Hoboken, one Peirce-Smith converters and one rotary anode furnace. The feed is composed of 83% copper concentrate and 17% metallic copper precipitates, which results in a feed average grade of 32% of copper content. The final products are 75,000 tonnes/year of copper anodes and 48,000 tonnes/year of sulphuric acid. At present, the plant is undergoing a modernization to expand the smelter capacity to 300,000 tonnes/year of green feed and increase the sulphuric acid production to 100,000 tonnes/year. This will be achieved with the installation of an El Teniente Converter and an expansion in the acid plant. The work began in November 1991 and is scheduled to be in operaton by March 1993. The paper provides an overview of the modernization plans and results achieved to-date.

Jan 1, 1993

By B. J. Jody

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

Jan 1, 1996

By A. Vahed

The Goro Nickel Project is situated in the Southern Province of New Caledonia. Inco Limited and Goro Nickel S.A. have developed a process that features the use of pyrohydrolysis to produce nickel oxide. The process treats a blend of laterites by Pressure Acid Leaching followed by solvent extraction of nickel and cobalt using Cyanex 301®. Purified nickel chloride solution is converted to high purity NiO product and 6M hydrochloric acid, which is recycled back to the SX circuit. In co-operation with Andritz AG, spray roaster and fluid-bed pyrohydrolysis technologies were examined for this purpose. Tests were conducted at the Andritz AG pilot plant in Vienna, Austria, and at Goro in larger scale installations. The latter served to establish process engineering design parameters for scale-up. Several process variables were investigated in both technologies and the off-gas characteristics were established. Fluid-bed pyrohydrolysis was selected for the Goro commercial plant, primarily because it produced a granular nickel oxide. The main focus of this paper is to outline the results obtained in pilot plant studies of liquid fueled fluid bed pyrohydrolysis for the Goro Project. Keywords: lnco Goro Nickel, Fluid Bed Pyrohydrolysis, Pilot Plant Tests

Jan 1, 2004

Novel techniques were developed to obtain samples from and make measurements in the shaft of the flash furnace at the Kalgoorlie Nickel Smelter. The data obtained was used to validate mathematical models of the burners and the reaction shaft. Particle, gas and wall temperatures were measured along with the oxygen potential of the molten particles. Collected particles were characterised by sizing, chemical analysis and optical microscopy. The region of the shaft immediately beneath the burner where the rate of change was most rapid received special attention.

Jan 1, 1993

By Jilai Xue, Jun Zhu, Baisong Li

"TiB2-C/C Function Gradient Materials (FGM) is used in cathode materials to improve aluminum wettability and melt penetration in aluminum electrolysis. In this investigation, FGM was tested for use as part of the cathode materials, where a 10 mm thick TiB2-rich layer was on the top as an Al-wettable surface, the TiB2-C layers in the middle as a gradient layer and the carbon on the bottom as a base. Electrical resistances ofFGM were determined in the temperature range of25- 9600C in argon atmosphere. The results show that the present of TiB2-C gradient layer can reduce the open porosity and the electrical resistance of the cathodes materials at elevated temperatures. The cathode samples after aluminum electrolysis usually demonstrates an increase in electrical resistance, but the application of FGM layer can compensate such an increase for certain extend due to less variation in porosity and lower the level of melts penetration.IntroductionCarbon is still used for aluminum reduction cathodes dominantly, but it has a poor wetting properties by liquid aluminum and the anode-cathode distance has to be kept about 4-5cm with an additional 1.3-2.0 V voltage drop [l]. TiB2 has better wettability by liquid aluminum with higher electrical conductivity and stronger chemical resistance to the electrolyte attack. And the wettability ofTiB2-C composites cathode on liquid aluminum can be also improved, while liquid aluminum can completely wet the cathode surface ifTiB2 content exceeds 27% [2-4]. However, during the process of TiB2-C composites cathodes preparation and aluminum electrolysis, the deformation by temperature variation or sodium penetration are great disparity between TiB2 and carbon due to their physical properties difference. This will accelerate the cathodes cracking and deterioration."

Jan 1, 2013

By A. Warczok

The heat transfer coefficient between liquid slags and solid surfaces is important for the design and operation of metallurgical reactors. An experimental technique developed for the purpose of measuring the heat transfer coefficient between liquid slags and solid metals is described. During the initial heating up of a Ni cylinder upon immersion in a liquid slag, a layer of frozen slag initially forms, then melts. The heat transfer coefficient measured during the initial rapid heat-up of the Ni cylinder, is approximately twice as high as the heat transfer coefficient measured during the final heat-up of the Ni cylinder subsequent of the liquidus temperature of the slag. The technique was tested in various melts i) NaNO3, ii) NaCl, iii) Na3AlF6 and iv) 2FeO*SiO2, giving consistent results. It was found that the heat transfer coefficient increases with increasing bath superheat and stirring. The heat transfer coefficient during the heating up following complete remelting of the frozen slag, is related to the slag superheat(AT) and the specific stirring energy(W) per kg of slag(E) as follows.

Jan 1, 1993

By Bradford C. Wesstrom

The extraction of metals from Copper Refinery Slimes may involve many different processes. This paper describes the use of pressure leaching for decopperizing of copper refinery slimes at the El Paso Refinery. Process equipment will be described, along with the process chemistry, unit operations and unit processes associated with the decopperizing process. Copper contained in the raw slimes ranges from 15-35%. After autoclaving less than 1 % copper remains.

Jan 1, 2000

By J. H. Huang

In this investigation, the selective precipitation of cobalt and molybdenum from Co-Mo aqueous solutions was studied in order to recover efficiently valuable elements from industrial effluents generated from a novel electrodeposition of nanocrystalline Co-based alloys process and reduce the effluent impact on environment. It was found that the behavior of cobalt in aqueous solutions was substantially affected by the presence of molybdenum. When adding 11.6 to 46.6g/L molybdenum to a 50g/L cobalt solution, the co-precipitation of molybdenum and cobalt started to occur at pH value of 3-4. However, without the presence of molybdenum, cobalt could only be precipitated out of the solution at about pH 6. Most of the molybdenum was found in the solid phase when the solution pH reached 5. After further increasing pH to greater than 7, the molybdenum dissolved back into the solution. Cobalt kept precipitating as the pH increased. When the pH was greater than 7, most of the cobalt was present in the solid phase. The chemical and physical characteristics of the precipitated materials were investigated by SEM, XRD, AAS and EDX. It was revealed that the precipitate was initially present as cobalt molybdate oxide hydrate and subsequently transformed as sodium cobalt molybdenum oxide. With further increasing the solution pH, the precipitate was transformed into cobalt hydroxide. Further investigation implied that most of molybdenum was chemically tied to the precipitate produced at the low pH, yet at the same time, physically entrapped at the high pH. The paper also presents the influence of reaction temperature and time on the precipitation process and kinetics.

Jan 1, 2003