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By J. R. Goode

There are at least a dozen methods of selectively removing cerium from a mixture of the rare earth elements (REE) including separation techniques based on the oxidation of cerium to the quadrivalent state. Several of the oxidation processes have been operated on a commercial scale, others have been tested and in some cases are part of proposed flowsheets. In this paper, we describe and compare the various methods. We also present preliminary estimates of the costs of early Ce removal and discuss recovery and purity aspects of the options.

By Manolete Mena

WC-Co nanocomposite powder is among the first group of materials with a promising potential for nanocrystalline-materials application. A chemical vapor synthesis (CVS) process that has previously been used for preparing the aluminides of titanium and nickel, and other metallic and intermetallic powders has been applied to the preparation of WC-Co nanocomposite powder. This CVS system was designed so that a tungsten precursor (WCl6 powder) and a cobalt precursor (CoCl2 powder) were separately fed into each evaporator in a reactor by means of specially designed powder feeders. The reduction and carburization of the vaporized chlorides by methane-hydrogen mixtures produced nanosized WC and Co composite powder. The product is a very uniform mixture of the constituent powders, which is important to ensure a high quality of the bulk cemented tungsten carbide product after consolidation. In the present work, the effects of reaction temperature, CH4 to WCl6 ratio, CH4 to H2 ratio, residence time, and Co content on the powder composition and particle size were determined. The products were characterized using XRD, carbon analyzer, and TEM.

Jan 1, 2006

By Manolete Mena

WC-Co nanocomposite powder is among the first group of materials with a promising potential for nanocrystalline-materials application. A chemical vapor synthesis (CVS) process that has previously been used for preparing the aluminides of titanium and nickel, and other metallic and intermetallic powders has been applied to the preparation of WC-Co nanocomposite powder. This CVS system was designed so that a tungsten precursor (WCl6 powder) and a cobalt precursor (CoCl2 powder) were separately fed into each evaporator in a reactor by means of specially designed powder feeders. The reduction and carburization of the vaporized chlorides by methane-hydrogen mixtures produced nanosized WC and Co composite powder. The product is a very uniform mixture of the constituent powders, which is important to ensure a high quality of the bulk cemented tungsten carbide product after consolidation. In the present work, the effects of reaction temperature, CH4 to WCl6 ratio, CH4 to H2 ratio, residence time, and Co content on the powder composition and particle size were determined. The products were characterized using XRD, carbon analyzer, and TEM.

Jan 1, 2006

By Cassandre Nowicki, Louis Gosselin, Carl Duchesne

"Quebec's primary aluminium production industry consumes roughly 39 TWh of electricity per year and is accountable for roughly 7 million tons of CO2 equivalent. By tapping only a small portion of waste heat and integrating it inside the production facility itself, we can significantly reduce GHG emissions and energy consumption. Although the amount of thermal waste can be adequately estimated by applying an energy balance to production processes, this provides very little information on the quality of waste heat and its potential for integration. A measure of exergy is required. Waste heat streams characterized by high exergy content may generally offer valuable incentives for recovery and integration. More generally, exergy values limit integration possibilities. An exergy analysis is provided for the aluminium electrolytic reduction process. This is meant to guide future heat recovery initiatives and energy efficiency measures.IntroductionCanada is one of the world leaders in primary aluminium production and 92% of its aluminium production capacities are located in the province of Quebec. In 2007, production capacity reached 2,786,000 tons in Quebec alone. Since it is estimated that 2.5 equivalent tons ofCO2 are released for each ton of aluminium produced in Canada, Quebec's aluminium production industry is accountable for roughly 7 million tons of CO2 yearly [1, 2]. Furthermore, with an average electricity consumption of 14 MWh per ton, primary aluminium accounts for 39 TWh of electricity per year in Quebec and this energy consumption represents 350 thousand tons ofCO2 equivalent [3, 4]. Natural gas consumption associated with primary aluminium production accounts for less than 1 TWh, but it represents an additional 350 thousand tons of CO2 equivalent [ 4].This work is meant to provide a tool to guide future efforts towards heat recovery and energy efficiency in the primary aluminium industry. Waste heat recovery and thermal integration can cut down both energy consumption costs and GHG emissions. In a primary aluminium production facility, waste heat represents roughly half of the energy input into the Hall-Heroult process. Tapping only a small portion of this energy could reduce natural gas and electricity consumption significantly. In order to evaluate how much of this energy is actually usable, we propose to apply an exergy analysis to individual transformation processes in an aluminium production facility, such that a potential to do work can be assigned to every waste heat flux. The approach will be described in the next section."

Jan 1, 2012

By Malti Goel

"Ferrous and non-ferrous metals industries are source of both direct and indirect greenhouse gas (GHG) emissions. Metal industry accounted for 29.7% of the total GHG emitted from the Indian industry sector in 2007. Aluminum is second largest contributor after steel. Indian Aluminum industry has been growing and is adopting several effective measures for better efficiencies through process change and waste utilization. Improvement in the energy efficiency can form the basis of monitoring reduction in emissions. Under the National Action Plan on Climate Change 2008, National Mission for Enhanced Energy Efficiency (NMEEE) aims to upscale the efforts to unlock the market for energy efficiency improvement on a public private partnership (PPP) basis. For a transition to low carbon economy industry is undertaking voluntary measures through scientific and technological innovations both in upstream and downstream sectors. In this paper an attempt is made to overview recent developments in Indian Aluminum industry as well as summarize scientific & technological challenges and prospects.IntroductionAluminum plays a vital role in industrial development. It is a substitute for different type of materials ranging from wood to copper and steel. The aluminum industry has high energy consumption and high contribution to greenhouse gases from carbon dioxide and perfluorocarbons (PFCs) emissions. It is estimated that CO2 equivalent burden of aluminum industry is about 1% of total anthropogenic emissions. The anticipated world growth rate is 3.5% for aluminum demand. Through measures to reduce both direct and indirect CO2 emissions, electricity consumption was reduced from 25 kWh / kg of Aluminum in 1998 to 15 kWh / kg of Aluminum produced in 2008. It is targeted to further reduce it to 10.8 kWh. Aluminum industry is also responsible to about 60% of all PFC emissions. The PFC emissions are harmful to environment, accumulate in surrounding vegetation and contaminate. Efforts to reduce PFC emissions from aluminum industry started early and reduced to 0.5-1 kg / tonne in 1990 [1] from 12-15 kg / tonne in 1940. Since 1990s to 2000 it further reduced to 0.2 -0.4 kg / tonne as seen in Fig. 1. The Global Aluminum Sustainable Development Initiative (GADSI), targets perfluorocarbon (PFC) specific emissions reduction of 80% for 2010 relative to 1990."

Jan 1, 2011

By T. Feldmann

Despite the ubiquity of applications for germanium, there is a lack of practically useful solubility data in acidic solutions. Previous studies were done at ambient temperature and only for commonly used acids (H2SO4, HCl). Hence, an investigation of the solubility of GeO2 in different acids was undertaken. Several inorganic and organic acids were studied in the concentration range of 1–11 mol/L and at 23, 40, and 60 °C. In the case of H2SO4 and HCl previous data was confirmed. Lower acidity resulted in a higher solubility for Ge at all tested temperatures. Tests done at 40 and 60 °C and low to moderate acidity levels, gave slightly increased solubility values at higher temperatures compared to 23 °C. This wasn’t the case at higher acidity levels, i.e., the solubility curves at different temperatures converge at high acidity. Lastly, a relationship of water activity and GeO2 solubility in different acid media was established.

By Zviad Kovziridze

The problems related to the production and research of SiC-Si3N4 composite are presented. The technology of producing the protective casings for tips and thermocouples is developed. Optimum composition charge and technological parameters are defined. The results of casing testing at production plants are presented.

Jan 1, 2006

By C. A. Morais

The present work describes the development of an efficient and relatively simple process to obtain high grade CeO2 from a mixed rare earth chloride solution. The process involves cerium oxidation and precipitation by addition of a KMnO4-NaCO3 solution. The experiments were carried out at room temperature (25 1° C). The results indicated that the major parameters affecting cerium recovery are the molar ratio of KMnO4/Ce, the initial acidity of the chloride feed solution and final pH of Ce(OH)4 precipitation. In strong acid solutions (pH < 1), the oxidation of Cl to Clo took place in addition to the oxidation of Ce(III) to Ce(IV), so increasing the permanganate consumption. Conversely, low acidity (pH >3) led to coprecipitation of the other rare earth elements. Under the selected conditions, cerium was selectively precipitated as ceric hydroxide, together with some manganese dioxide. Further purification was carried out by the dissolution of Ce(OH)4 in HCl, followed by precipitation as cerium carbonate. The filtrate was neutralised with a Na2CO3 solution in order to recover the associated rare earth elements for further separation. The final product, assaying 99.7 % CeO2, was obtained with a recovery of nearly 100%.

Jan 1, 2003

By Ting Lei, Mingjun Rao, Guanghui Li, Tao Jiang

"With the rapid development of iron and steel industry, the supply of iron ores can not meet the present demand for iron and steel industry in China. Large reserves of oolitic hematite have been discovered with low iron grade (30% ~ 45%) and high phosphorus content (0.4% ~ 1.8%). Traditional processes for utilization of this ore are characterized as either high cost or low dephosphorization. In this study, sodium salts-modified paigeite (SSMP) was added to enhance on the dephosphorization of high-phosphorus oolitic hematite by using reduction roasting followed by magnetic separation. Various parameters, including the amount of SSMP, reduction time,reduction temperature, grinding fineness and the magnetic field intensity were investigated. As a consequence, a magnetic concentrate of metallic iron powder with total iron grade of 93.2% and phosphorus content of 0.08% was obtained under the optimal conditions. The results also provide a potential avenue for the comprehensive utilization of paigeite ore.IntroductionOolitic hematite is currently recognized as one of the most refractory iron ore resources in the world. Over 4.0 billion tons of reserves of such resources have been found in China, and more than 10 billion tons in the long-term. This kind of ore is characterized as low iron grade (30%~45% TFe) and high phosphorus content (0.4%~1.8% P), as well as fine particle size distribution of ferrous minerals (the size distribution varies from 5~30 µm, even less than 2 µm) and the complex association between iron and other gangue elements [1~5]. The unique structural characteristics of the high phosphorus oolitic hematite make it difficult to obtain high iron recovery and good dephosphorization efficiency by using the conventional processes [1,2]. Traditional processes are characterized as high cost and low dephosphorization for oolitic hematite beneficiation [9~15]."

Jan 1, 2012

By J. Rajesh Kumar

The extraction equilibrium study of tetravalent platinum was carried out using tri-octyl/decyl amine (Alamine 336) and bis(2,4,4-trimethylpentyl) monothiophosphinic acid (Cyanex 302) in kerosene from hydrochloric acid media to investigate their extraction capacity, since they have different donor atoms, ?N? and ?S?. Their distribution equlibria were studied as a function of acid, extractant, diluents and temperature. The title metal shows the inverse behavior at higher acid concentrations. Extraction of tetravalent platinum increases with increase of extractant concentration. The plot of log D vs. log [Extractant], mol.L-1 is linear with slopes 1±0.3, indicating the association of one mole of extractant with the extracted metal species. Stripping of metal from the loaded organic (LO) with mineral acids and bases such as hydrochloric, sulphuric, nitric acids and ammonia, hydrogen peroxide, sodium hydroxide, thio- urea were studied. Regeneration and recycling capacity of Alamine 336/Cyanex 302 and extraction behavior of associated elements was also studied.

Jan 1, 2009

By Aliye Arabaci

In the present investigation, an attempt has been made to study the reduction behavior of composite pellets consisting two different types of iron oxide fines (high and low grade) and coke or lignite fines as reducing agents. The reduction experiments were carried out under isothermal conditions and constant flow of nitrogen gas in the temperature range of 900 ? 1100 oC. The variables investigated are the reduction temperature, Cfix/Fe3O4 ratio, reduction time and reductant type. In the experiments carried out with Sivas Divrigi A head magnetite ores (high grade) at a temperature of 1100 oC, for 40 minutes and on the condition that Cfix/Fe3O4 ratio is 0.2, in which lignite and coke fines were used as reductant, degree of reduction was obtained as 91 % and 86 %, respectively. Whereas, in the experiments realized with Malatya-Hekimhan-Hasançelebi magnetite ores (low grade) on the same conditions by using lignite as the reductant, around 60 % degree of reduction was found.

Jan 1, 2008

By Hiroyuki Matsuura

Treatment of electric arc furnace (EAF) dusts has become an important issue from the viewpoint of the environmental protection and recycling of variable resources because these dusts contain considerable amount of zinc and lead. A new recovery process of these metals has been proposed, in which the metals in the dusts react with waste polyvinyl chloride to form metal chlorides. Therefore, it is important to clarify the physicochemical properties and behaviors of zinc, lead and those chlorides and oxychlorides. In the present study, the kinetics of chlorination of ZnO, PbO and ZnFe2O4 mainly contained in the EAF dusts were investigated at 1023 K to 1273 K with Ar-O2-Cl2 gas. Based on these results, the selective chlorination and evaporation process of zinc and lead from the mixture of Fe2O3-ZnFe2O4-ZnO-PbO was examined and the high efficiency of selectivity has been demonstrated.

Jan 1, 2006

By Evgueni Jak

Recent advances in analytical, experimental techniques, and computer-based theoretical modelling of fundamental properties and elemental processes, provide new opportunities to develop the next level of whole-of-reactor pyrometallurgical furnace models. These models have the potential to significantly improve the prediction of, and adding value to, industrial operations. In non-ferrous smelting, the starting point of these models is the development of multicomponent thermodynamic databases for gas-slag-matte-speiss-metal-solids phases supported by systematic experimental research. The whole-of-reactor-models additionally should take into account kinetic processes taking place at micro- and macro- scales, and other key factors. Examples of applications of the latest research tools and modelling approaches to analysis of industrial flash and top submerged lance (TSL) sulphide smelting processes are presented. Different levels of industrial modelling are discussed from elemental local reactions, through general and more detailed whole-of-reactor-models, to plant sections and further to whole plant operation models. Some principles for development of pyrometallurgical reactor models are discussed.

By Antoine Allanore, Luis A. Ortiz, Donald R. Sadoway

"The steelmaking industry has drastically reduced its energy consumption in the last fifty years, and today’s technologies are considered to operate at their optimal efficiency with respect to energy needs. To cope with new constraints related to greenhouse gas (GHG) emissions, a change of paradigm is necessary. One of the promising technologies that could be deployed to help reach CO2 mitigation targets relies on the intensive use of electricity: molten oxide electrolysis (MOE). This paper presents the key process parameters that need to be tuned to address the practical needs for both high productivity in a steelmaking reactor and for an energy efficient process. Herein we show that contrary to common perception, the electrolysis process for ironmaking requires less energy than today’s chemical reduction route. Furthermore, we prove that most of the energy that must be provided to operate the electrolytic iron production cell is thermal energy which is readily generated by joule heating during electrolysis due to large currents being passed through the electrolyte. The energy consumption of the electrolysis cell is therefore shown to be highly dependent on the cell configuration and the chemistry of the electrolyte. As a consequence, the CO2-impact of the technology strongly depends on both the power production mode and the technological choices for design of the process, including cell configuration. Surprisingly enough, even when the electricity generation is not carbon-free, MOE still appears to be viable from the perspective of reducing GHG emissions providing sound reactor design considerations are made.IntroductionIn the context of greenhouse gas (GHG) emissions mitigation, the steelmaking industry is considering several techniques that could sustain the efforts and progress achieved by this sector in the last decades [1]. A recent report [2] on potential routes for low-CO2 steelmaking highlighted for all techniques both the strong dependency of CO2 emissions on electric power production mode and the need for a decrease in energy consumption per tonne of steel. Incited to innovate with respect to this last criterion, the steel industry considers electrolysis to be a promising technological solution, and in particular the molten oxide electrolysis (MOE) process. This process conducts electrolysis in a mixture of oxides that dissolve the iron oxide feed, which by the action of electric current is decomposed into liquid iron and oxygen gas. The opportunity for reduction in energy consumption during steelmaking by MOE is commonly attributed to the “direct” pathway from iron oxide to liquid metal offered by the use of a molten oxide melt and operation at a temperature above the melting point of iron, ideally 1600°C, to provide enough superheat for tapping the molten iron product:"

Jan 1, 2011

By Na Wang, Chao Du, Yao Zhang Shuqiang Jiao, Hongmin Zhu

"Na2NbAlO5 was synthesized using Nb2O5 and NaAlO2 as raw materials in molten NaCl-CaCl2 by a solid reaction. With an addition of sodium into the melts, Na2NbAlO5 was subsequently reduced to form NbAl3 intermetallic compound with a particle size of 50-300nm.IntroductionThe intermetallic compounds of niobium aluminides have been a subject of research interests as high temperature materials because of their properties such as high melting temperature, large specific strength at elevated temperature, good resistance to high temperature oxidation, low density and large ductility [1,2]. They are applicable for turbine blades in aircraft engines and stationary gas turbines [3,4].In recent years, the methods of powder synthesis have been widely discussed. There are many methods to synthesis intermetallic compounds such as conventional melting and solidification [5], powder metallurgy [6,7], reaction sintering [8] and reaction sintering with prior mechanical activation [9,10]. There is a prominent weakness in such methods that they use metal to produce intermetallic compounds by the means of diffusion reaction. Although the metal can diffusion sufficiently, it is still hard to avoid maldistribution of the constituents which impairs the properties of the materials."

Jan 1, 2012

By John Wallace

"Monitoring compound semiconductor crystal growth using multifrequency eddy currents for sensing illustrates some of the extreme problems of measurement and interpretation that are not often seen in metallic systems. Using sensor arrays and scanning sensors have produced a qualitative and quantitative understanding of some of the high temperature electrical conductivity mechanisms in several compound systems. A detailed review of the CdTe/CdZnTe data is presented showing some of the complexity in the data as opposed to what is found in elemental semiconductors.HistoryThe most common goal in the use of eddy current measurement in crystal growth is to deter-mine the curvature of the liquid solid interface during growth to test if the heat transfer estimates of the thermal design were adequate for single crystal growth[l]. This aim could be met but represented only a small fraction of the data that was produced observing a growth cycle. A secondary consideration was what could be discovered in the recorded data about the growth and subsequent heat treatment as the boule cooled. This is usually a more difficult task because a crystal growth process is not a controlled experiment so much as a process that continually sees modification. Using a sensor arrays or a scanning loop has produced a qualitative and quantitative basis for understanding some of the high temperature electrical conductivity mechanisms. The implication of the these measurements of electrical conductivity variations are important in that they reflect the complex defect states that will occur on cooling and heat treatment following crystal growth. In contrast to the complex behavior of the conductivity of these compound semiconductors in the solid and liquid state we have the very well characterized system silicon to compare. Initially the interest on using eddy currents to monitor compound semiconductors came from G. Westphal at the Texas; Instruments Company in 1987 to monitor aspects of growth and compounding of GaAs. This was followed by work on solution growth of HgCdTe with D. Witter. The initial interest in the use of eddy cur-rents for monitoring CdTe crystal growth came from Prof. Wilcox at Clarkson University in the practical interest to determine and control the crystal interface curvature during vertical brigdeman growth. The first actual work was done by one of his former students. G. Neuge-bauer at the II-VI Corporation which was carried on by G. Rosen at Clarkson and R. Shetty at II-VI Corporation and with A. Socha at Johnson-Matthey Electronics. The work on CdTe extends over four years and yielded sufficient data to allow one to evaluate the utility of the information produced as compared to what could be obtained from monitoring an elemental semiconductor such as silicon."

Jan 1, 1997

By Liang Li

Thermodynamic analysis and experiments were conducted in order to verify the feasibility of preparing crude titanium tetrachloride (TiCl4) via the carbochlorination of low-grade titanium slag in molten salt. Titanium slag, assaying 74.6 wt% TiO2 with high calcium and magnesium oxide impurities, was treated by an optimized carbochlorination process in NaCl molten salt. These impurities in the titanium slag were chloridized simultaneously, and chlorination products FeCl2, MnCl2, MgCl2, CaCl2 and CrCl3 were collected in the furnace slag. XRD and SEM/ EDS analysis of residue shown that SiO2 and Al2O3 in titanium slag were difficult to chlorinate completely. Theoretical calculations and industrial-scale experimental studies reveal the content of TiCl4 in the products was more than 98.8 wt% and thus proved the feasibility of utilizing low-grade titanium slag for TiCl4 preparation by molten salt chlorination technology.

By Li Rongxing

A general regular solution model put forward in this paper defines a general interaction parameter that includes both composition and temperature dependence. On the basis of this model, analytic express of solution excess properties was obtained by least square fit using the composition and temperature relations in binary alloy phase diagram. After some solution excess properties analytic expresses of correlated binary alloy system obtained, the analytic express of ternary alloy system could be obtained by superposition of general geometrical model. The ternary alloy system Pb-Sn-Zn has been predicted in terms of this method and the result was very in agreement with actual measured value.

Jan 1, 2006

By M. F. Chambers

Neodymium metal was electrowon from a molten-chloride electrolyte at 650° C using a molten-metal cathode. A 50 mol pct NdC13-50 mol pct KC1 mixture served as the electrolyte. Binary metal alloys of &apos;Mg with Zn and Mg with Cd were used as molten cathodes. Under the best conditions, current efficiencies were 90 pct with a Mg-Zn cathode and 80 pct with a Mg-Cd cathode. Vacuum distillation was performed at 1,100° C for 30 min under a vacuum of 10-3 to separate the cathode metals from the neodymium. Neodymium metal of 99.9+ pct purity was recovered from the Mg-Cd alloy cathode. Almost 2 pct zinc remained in the neodymium recovered from the Mg-Zn alloy.

Jan 1, 1989

By Shivendra Sinha

Total pressure oxidation (TPOX) is widely outreached leaching practice for base metals from sulfide minerals, wherein high temperature (T ∼ 200 °C) and oxygen pressure (pO2 ∼ 25 bar) are required. These aggressive conditions intensify the oxygen mass transfer, and therefore facilitate metal dissolution. However, challenging-cum-negative aspects of such practice are energy and material intensive requirements and high oxygen demand. Thus, the present study explores the novel emulsified medium for enhancement of oxygen mass transfer, which assists faster metal dissolution at significantly lower temperature and pressure condition. It is possible to achieve quantitative dissolution (>95%) of Cu, Ni and Co from mixed sulfide minerals at T ∼ 95 °C and pO2 ∼ 2 bar using an emulsion of 2.5% (v/v) n-Hexadecane in dilute sulfuric acid. In addition, n-Hexadecane was found to be inert, stable and immiscible in a pressurized leaching system, thus can be easily separated and recycled in subsequent leaching stages. Thus, this study offers an energy efficient route for low temperature-pressure leaching of sulfides.