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By Shawn A. Cefalu, Matthew J. M. Krane, Kent J. VanEvery

"Segregation during electroslag remelting (ESR) of a nickel-chromium-molybdenum alloy (Ni-8 wt% Cr-25 wt% Mo) has been modeled. Features of the model include species transport and AC electromagnetic effects coupled with fluid flow, heat transfer, and solidification. The effect of varying ingot diameter and melt rate, on macrosegregation patterns, local solidification time, and liquid pool profiles obtained from this model are demonstrated. The results show that the macrosegregation in the ingots correlates to the filling velocity.IntroductionElectroslag remelting (ESR) is a secondary melting process used to refine the chemical composition and the microstructure of metals. Macrosegregation of solute elements causes defects in ESR ingots, including freckles and the maldistribution of phases. These defects are not correctable through heat treatment due to the large length scales over which they occur. However, the frequency and distribution of these defects may be minimized, or even prevented, through process control based on an understanding of the conditions that lead to their formation.In the past, studies have been conducted on the effect of the process parameters on the shape of the melt pool and the thickness of the mushy zone [1-7]. In these studies, the shape of the liquid pool is determined by consideration of the heat and fluid flow induced by electromagnetic (Lorentz) force and thermal buoyancy. The transport of solute and the resultant solutal buoyancy effects were not considered in these macroscopic models. Defect formation is tied to formation of secondary phases (e.g., freckling and white spots in nickel superalloys) [5,8]. In cases where secondary phase formation is calculated (e.g., [6]), phase fractions are determined using a micro-scale model given the local solidification time (LST) and local thermal history from the macroscale model.Using the local thermal history from the macroscopic transport model to predict microstructure increases the importance of the accuracy of those results. This investigation models the macrosegregation of molybdenum during the ESR of a Ni-Cr-Mo alloy. The effect of macrosegregation on pool shape and depth is demonstrated, along with its effect on the local solidification time. By comparing the relative effects of the melt rate and ingot radius, a better understanding of the factors that affect macrosegregation, and ultimately secondary phase formation may be obtained."

Jan 1, 2004

By Hojat Naderi

In this research assisted leaching of chalcopyrite using sodium peroxodisulfate was studied. Electrochemical techniques such as Tafel analysis and electrochemical impedance spectroscopy (EIS) were used to investigate the surface reactions of a chalcopyrite electrode in the presence and absence of Na2S2O8. According to the results, addition of sodium peroxodisulfate increases the current exchange of the corrosion process and prevents the formation of a passive layer on the surface of the electrode. EIS tests show the trans-passive dissolution of the passive layer on the chalcopyrite electrode in presence of Na2S2O8. Equivalent electrochemical circuits were modeled for Na2S2O8-free and -containing solutions and the model parameters were compared to determine the effect of S2O8 2− on chalcopyrite dissolution. Copper dissolution from pure chalcopyrite mineral and chalcopyrite concentrate was carried out using 15 g/L sulfuric acid solution with and without Na2S2O8. Simultaneous presence of 10 g/L ferric ion and 40 g/L peroxodisulfate salt results in about 40 and 18% of Cu extraction from chalcopyrite concentrate and pure chalcopyrite mineral, after 96 h, respectively.

By H. C. Roland Kammel

Stannous sulfate electrolytes are widely used nowadays in electrolytic tin production. Characteristic features of this electrolysis process are that dense cathode deposits can only be obtained by additions of organic additives and that so called ?black mud is formed on the anode surface which leads to an increase in cell-voltage. In order to prevent excessive cell-voltages or oxygen evolution the black mud has to be removed periodically. Studies in laboratory scale have been performed about the effect of different organic additives on electrolytic tin deposition and the formation of surface layers on pure and industrial tin anodes. Results reveal that organic addition agents are effective in reducing cathode roughening as well as extending the covering time of the anode ?by black muds.

Jan 1, 1985

By A. Cullaj

Several industrial sites suffer from the contamination of soils from heavy metals, which are emitted among others by anthropogenic mining and metallurgical activities. Effective and economic physicochemical technologies for remediation of these sites remain complicated and costly. A new alternative remediation technique is the so-called phytoremediation. This is based on the ability of some plants to accumulate very high concentrations of metals from soils and thus providing the basis for a remediation of the contaminated sites. This technique as an emerging branch of natural biotechnology, has several advantages compared to the sophisticated physicochemical techniques of soil remediation. It is not only environmentally friendly but also its costs are quite low since it is solar driven. Furthermore plants can accumulate metals to such levels that the mineral recovery maybe feasible even in conventional Ni refinery or smelting operations. In this work, thc potential of many plants to accumulate nickel has been investigated in order to identify the species which offer the best phytoremedial potential for nickel contaminated soils in Albania. Field surveys have been made in five nickel-containing sites in order to identify the nickel tolerant species that have spontaneously grown in contaminated soils. Atomic Absorption Spectrometry measurements were carried out on 145 different plants collected. 16 of them were identified as having an hyper ability to accumulate nickel since they contained more than 10 000 mg Ni per kg (DW). Seven taxa are of Alyssum genus and one of Bornmuellera genus of Cruciferae. The highest accumulation of nickel was present in aerial parts of Alyssum murale var. chlorocarpum Hausskn (25 500 mglkg or 2.5%) and Alyssum markgrafli O.E. Schulz (23 700 mg/kg or 2.37%). The seeds germinated are more evidenced at A.m.var. chlorocarpum, about 63%. These plants are suggested as the most promising species to be used for phytoremediation purposes in nickel contaminated soils and phytoextraction of nickel.

Jan 1, 2003

By S. R. Hutchins

Several refractory sulfide and carbonaceous gold ores were examined to determine whether microbial pretreatment could be used to enhance gold recovery. Test samples were biologically leached using unique. thermophilic microorganisms to solubilize iron sulfide minerals. Gold recovery from sulfide ores and concentrates was enhanced following pretreatment with the thermophiles; responses varied widely for the individual materials. Although bioleaching had little effect on the preg-robbing characteristics of the carbonaceous gold ores, cyanidation of the bioleached residues yielded higher gold recoveries than cyanidation of the native ore. By combining bioleaching with abiotic processes designed to inhibit preg robbing, gold recoveries of 83-98% were obtained from carbonaceous ores yielding 10-50% gold recovery by direct cyanidation.

Jan 1, 1987

By H. Y. Sohn

"The nonferrous production industry has gone through a remarkable transformation in recent years in terms of developing and adopting new technologies. Technology innovations have largely been driven by the need for greatly improved environmental protection in addition to increased productivity. One of the most notable aspects of the new technologies is their ability to reduce the emission of sulfur and other pollutants to extremely low levels.The current industry trends towards more environmentally friendly technologies are bringing about additional benefits of developing more efficient, technically advanced, and continuous processes in closed reactor vessels. Key aspects of these modem trends include the use of increased oxygen enrichment in the process gas, better process control, reduced manpower requirements, and plant operations with more skilled personnel.Computer simulation and modeling of complex processes have become more reliable, realistic, and thus increasingly useful in metal production. Some of the notable examples are reviewed.Finally, the need and advantages for value-added production in the nonferrous industry are discussed.I. IntroductionMost recently commissioned technologies for nonferrous metals production have been developed largely in response to environmental concerns. One of the most remarkable improvements made by the nonferrous industry in the last decade has been the rapid increase in sulfur capture. Before the start of the last decade, 90% capture of sulfur was considered good. Since then, strict emission regulations have become the norm in advanced societies, although smelters in many parts of the world still operate with limited pollution control. Other emissions and discharges have also been substantially reduced, resulting in much improved working conditions and worker hygiene in addition to the overall environmental protection. The development of the more environmentally friendly technologies has accompanied other advantageous advances made in the nonferrous industry, i.e., the trend towards more gas-tight, continuous processes and larger plants. This has increased the competitive edge enjoyed by the industry in the industrial countries, offsetting the higher costs of labor and pollution abatement that they have to overcome in those countries. Experience has shown that clean technology often leads to a profitable business, because its adoption forces the concomitant advancement of related technologies in addition to the avoidance of penalties imposed by the public on pollution-prone industries. Needless to say, there are other driving forces for new technologies such as reduction of operating and capital costs, improved product quality, and energy considerations in terms of reduced consumption and utilization of readily available sources."

Jan 1, 2000

By Zhao wen Wang, Ramana G. Reddy, Min Li

"The electroreduction of Co(II) in l-butyl-3-methylimidazolium tetrafluoroborate (BMlMBF4) ionic liquid was investigated by cyclic volatrnmetry at 353 K. The results show that the reaction of Co(II) to Co is irreversible in one step with two electrons transferred. The diffusion coefficient of Co(II) was estimated to be 7.6 x 10-8 cm2 s·1 at 353 K. Then the electrodeposition of cobalt was studied at different cathodic potentials (-0.80 to -0.95 V) and different temperatures (333 to 363 K) in BMIMBF 4 containing 0.20 mol L-1 Co(BF4)z. The deposits were characterized using scanning electron microscope (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffraction (XRD). SEM images show that a uniform, dense, and compact deposit was obtained at -0.80 V and 333 K. The deposits were identified as high-purity metallic Co for all experiments by EDS and XRD.IntroductionCobalt is known as a hard magnetic material and cobalt alloys have been shown to have excellent magnetic properties with adequate mechanical durability and corrosion resistance, which are needed for high performance magnetic recording applications [1-4]. The electrodeposition of Co alloy in the aqueous solution is generally difficult because of the narrow electrochemical potential window of water, which leads to the low current efficiency and worse quality of deposits due to the hydrogen embrittlement. Thus, aprotic ionic liquids (ILs) are expected to be the ideal alternative media for electrodeposition of cobalt or its alloy since ILs usually provide a wide working potential windows, negligible vapor pressure, and acceptable conductivity for electrolysis without the occurring of hydrogen evolution [5, 6]."

Jan 1, 2014

By R. Boom, Y. V. Meteleva-Fischer, B. Kraaijveld, H. Kuntzel

"Segregation of impurities during refining of metallurgical grade silicon (MG-Si) is an option to produce solar grade silicon (SG-Si). Directional solidification is a last step in production of SG-Si effective for removal of metallic impurities. The possibility is investigated to use metallic impurities originally present in MG-Si for removing boron and phosphorus. MG-Si has been treated using two methods: 1) alloying with calcium and 2) refining with Na2O-CaO-SiO2 slag, both by controlled cooling. The microstructure of silicon and the impurities distribution have been studied before and after the treatments. Using EPMA phosphorus and boron have been detected in 1-2 wt% concentration range in several intermetallic compounds in grain boundaries after both treatments. This observation points to a different possible mechanism of silicon refining from boron and phosphorus. Controlled cooling improves migration of phosphorus and boron to the silicide phases in grain boundaries, which can be removed by acid leaching treatment.2. IntroductionStandards for silicon solar cells and growing demand on “green” energy require economical and efficient route to the production of solar grade silicon. Refining of cheap metallurgical grade silicon is one of the promising options, where application of existing metallurgical approaches can result in cost-efficient production on industrial scale. Focus in refining is on impurities, which are most difficult to remove: B, P, Al, Ti, due to their large segregation coefficient in silicon and low vapour pressure [1]. Moreover, more environmentally friendly technology in comparison to the traditional Siemens process [2] will be in accordance with societal needs. Based on properties of common impurities in metallurgical grade silicon, alloying refining and slag refining are suggested as competitive techniques having potential effect on removal of impurities harmful for conversion of solar energy [3, 4]. Alloying with Ca followed by acid leaching was found to be effective for removal of Fe and Ti from silicon [5] and to enhance also removal of boron [6] and phosphorus [7, 8]. In the work of Inoue et al. [8] drastically increasing removal of phosphorus from silicon has been observed with an increase of Ca content and a thermodynamics-based explanation was provided. Since phosphorus has been found to condense in the secondary precipitate mainly composed of CaSi2, it can be removed together with iron and titanium by consecutive acid leaching treatment. Slag refining is one of the metallurgical methods proposed to be effective for refining of metallurgical grade silicon from boron [9, 10]. Slags with additions of the following oxides to silica have shown positive effect on removal of boron: CaO [11-13], Na2O [11,14]. Mechanism of slag refining from boron is based on oxidation of boron followed by its incorporation in the slag network [9,11]; the same mechanism is suggested for refining from phosphorus taking into account that oxides of boron and phosphorus are known as network-formers [15]."

Jan 1, 2012

By Vladimiros G. Papangelakis

During the past five years, chemical modelling work at the University of Toronto has elucidated the role of soluble magnesium on the autoclave acidity and has demonstrated why feeds rich in magnesium, and other divalent metals, require more than the stoichiometric requirements in acid to produce a leaching performance comparable to that of low magnesium feeds. This understanding has allowed the calculation of acid additions to the pressure acid leach (PAL) on a less empirical basis. Optimizing acid additions to the PAL confers savings in neutralization costs, ensures high productivity and minimises corrosion problems. Hence, our picture of the solution chemistry inside the autoclave during the PAL process has been substantially improved and is reviewed here. Experimental techniques based on solubility and direct acidity measurements that support the theoretical predictions are presented. Concepts of chemical modelling of electrolyte systems at high temperature and software issues are also discussed. Finally, a better understanding of the solution chemistry at temperature has led to better kinetics models because all metal dissolution and precipitation reactions are acid driven and controlled. . Therefore, reactor modelling efforts by our group are also presented and a reactor model with very good performance, as compared to pilot-plant data, is also made here. Finally, in spite of the above success in PAL solution chemistry and reactor modelling, significant challenges lie ahead in theoretical data gaps and instrumentation; these are also discussed in this paper. Keywords: Laterites, process modelling, pressure acid leach, solution chemistry, chemical modelling, reactor simulation

Jan 1, 2004

By N. Kanari

The thermal decomposition studies of two zinc basic carbonate samples were carried out up to 400 "C by thermogravimetric analysis, boat experiments and differential scanning calorimetry measurements 'DSC'. The initial samples and the solid decomposition products were analyzed by scanning electron microscopy, x-ray diffraction and laser particle size analyzer. The thermal decomposition of both samples started at about 150 "C and the rate of decomposition became significant at temperatures higher than 200 "C. The apparent activation energies 'Ea' in the temperature range 150-240 "C for sample decomposition were between 132 and 153 kJ1mole depending on the sample origin. The XRD analyses of the intermediately decomposed samples and the DSC results up to 400 "C suggest that the decomposition reaction probably occur in a single step.

Jan 1, 2002

By M. C. Furerstenau

Adsorption behavior of various surfactants on sulfide minerals is very much affected by the nature of the surface of the mineral. Since sulfides are naturally meta-stable, oxidation occurs when they are exposed to air, especially in aqueous environments. As a result. oxygen assumes a major role in sulfide flotation. Mechanisms of adsorption of various thiol collectors on sulfide minerals have been reviewed. The electrochemical behavior of various sulfide minerals has also been reviewed. Flotation behavior of galena, chalcocite, sphalerite, pyrite, chalcopyrite and pentlandite has been presented together with the. flotation of copper sulfide- nickel sulfide ore.

Jan 1, 1993

By S. A. Shuey

The present industrial practice used to separate aqueous cobalt from nickel is multistage solvent extraction processing. This paper describes a different but simpler treatment technology. The proposed technology has been applied to cobalt/nickel hydroxide intermediate solids produced from the treatment of Electrochemical Machining (ECM) waste sludge, The process consists of dissolving the cobalt/nickel hydroxides in basic cyanide solutions. Cobalt and nickel form aqueous .solution metal cyanide complexes. Nickel can be selectively precipitated from the solution as a nickellic hydroxide solid. Cobalt can be recovered from the leach solution by precipitation of a cobaltous/cobaltic cyanide double salt. The double salt product can then be subsequently treated to produce an appropriate cobalt product. The process chemistry, proposed fiowsheet and preliminary reagent costs are presented and discussed.

Jan 1, 1998

By Yuanbing Ling

Keywords: Calcium sulfate, Sulfuric acid, Phase transformations, Thermodynamic analysis As part of a boarder research project, seeking the development of a cost-effective process for direct production of the high value material, -calcium sulfate hemihydrate, from sulfuric acid at atmospheric as opposed to elevated pressure conditions, the fundamental work presented here has been undertaken. This includes experimental monitoring of phase transformation reactions and thermodynamic analysis of the relationships among the various phases, namely, calcium sulfate dihydrate, hemihydrate and anhydrite in aqueous sulfuric acid solution at temperatures ranging from 20oC to boiling point.

Jan 1, 2004

By Guohui Zheng

The ever increasing quantities of solid wastes generated by various industries are at the source of the growing need for proper waste disposal methods. Thermal treatment of combustible wastes is a proven technology which permits the reduction of hazardous material having to be landfilled. However, this method is not universally applicable to waste disposal. For example, the transferal of heavy toxic metals into the thermal remediation products is a major issue of public concern. This paper focuses on the analysis of morphology changes from solid sludge to ash which is a product of the sludge combustion. The morphological parameters analyzed were particle size and external surface. They were determined using Jeol 840 Super Probe. The experiments were conducted in a computer-controlled high-temperature combustion system consisting of the thermogravimetric furnace coupled with Fourier transform infrared spectrometer (TGA-FTIR). Sludge particles were made of complex fibers trapped in the aluminosilicate matrix. At low temperatures, up to 680 K, the solid residue looked similar to the initial sludge. Between 680 K and 1180 K the sludge underwent intensive burning and steadily changed into powdered ash. At the temperature of 1050 K the ash was composed of separate, flat flakes with sizes ranging from 5 to 20 um. At 1470 K the flakes aggregated into large particles. The surface observed at 1670 K was a mixture of mullite crystals. Such structure could result from the solidification of the ash material after its melting. Morphological changes influenced the distribution of metals in the solid residue. For example, Cr was concentrated in small aggregates. Such distribution should allow for recovery of valuable metals from the solid waste residue.

Jan 1, 1996

By S. N. Monteiro, C. M. F. Vieira, A. P. N. M. de Sa, J. P. D. Vitorino

"This work has as its objective to characterize an ash waste and to evaluate its incorporation into a clay to produce bricks and roofing tiles. The waste is a type of fly-ash resulting from the incineration of a selected part of urban garbage, which is basically constituted of organic matter and plastics. The waste was submitted to mineralogical and chemical characterization. Compositions were prepared with incorporation of the waste in amounts of up to 20wt.% into athe clay. Rectangular specimens were prepared by extrusion and fired in a laboratory furnace at 900°C. The physical and mechanical properties evaluated were: linear shrinkage, water absorption and flexural rupture strength. The results showed that the waste is predominantly composed of quartz and calcium compounds. The incorporation of the ash was deleterious to the evaluated properties of the clay. It is suggested that the incorporation should be made in amounts below 5wt. % to avoid deleterious effect in the mechanical strength and water absorption of the clayey ceramic.IntroductionThe world attention has turned to a subject of great concern today, the production and disposal of large amounts of industrial wastes as well as wastes of various sources. When deposed in an unsuitable place, these wastes can cause considerable harm to human health and to the environment. Our planet suffers with air pollution, groundwater and soil contamination as well as silting of rivers and lakes with the growing amounts of our society wastes.The recycling of waste materials is of great interest to the industries, mainly due to the environmental agencies legislation. One of the practices for correct disposal of these wastes being investigated is to incorporate into red ceramics, such as bricks and roofing tiles. The natural variability of the characteristics of the clays associated with the relatively simple processing techniques and also the low performance required for the products allow the presence of relatively high levels of impurities in clayey ceramics."

Jan 1, 2011

By K. Alibhai

Greek laterites, which generally had nickel concentrations of < 1 %, are amenable to chemical leaching,. although there is considerable variability in the ease of leaching with different ore types. With low grade ores(< 1 % Ni content); >70% of the nickel was leached in columns with a strong selectivity for nickel over iron. Heterotrophic microbially assisted leaching could be a viable alternative to classical hydrometallurgical and/or pyrometallurgical techniques, with a very high recovery (greater than 80% ) being found with some of these mineral microbial interactions. Critic acid was probably the effective chelating agent.

Jan 1, 1991

By Patrick R. Taylor

A non-transferred arc thermal plasma assisted cyclone reactor has been designed, built and operated to evaluate its use in vitrification of wastes. Simulated waste (liquid, slurry or fine particulate) is injected near the plasma flame, where nearly instantaneous dehydration and calcination reactions happen. A non-transferred arc plasma torch was attached tangentially to the cyclone and is utilized as both an enthalpy source and to provide the gas velocities required to generate the cyclonic gas flow patterns. The closed top cyclone flow sends the solid particulates to the wall, where they are captured by a thin film of molten glass that is injected as a powder at a position lower in the reactor. The molten glass is then collected in a crucible. The feasibility of simulant injection directly into the flame zone and its effect on electrode lifetimes has been studied. Several candidate refractory systems have been evaluated for their suitability for extended use under the demanding conditions present in the cyclone reactor.

Jan 1, 2002

By Zhigan Deng

Cooling crystallization was used to separate iron (III) and nickel (II) from acidic sulfate solution produced by leaching of molybdenum-nickel black shale. The effect of K2SO4 concentration, crystallization temperature, solution pH and crystallization time on recovery of nickel (II) and precipitation of iron (III) was investigated, in order to obtain effective separation of nickel and iron. The optimum parameters determined were as follows: 200 g/L K2SO4, 10 °C crystallization temperature, solution pH of 0.5 and 24 h crystallization. Under these conditions, 97.6% nickel (II) was recovered as K2Ni(SO4)2, 6H2O crystals and only 2.0% of the total iron (III) was precipitated. Recrystallization yielded K2Ni(SO4)2, 6H2O crystals with a purity of 98.4%.

By A. S. Rao

In the original roast-leach-electrowin (RLE) circuit at the Chambishi Cobalt Plant, commissioned in 1978, the separation of nickel and zinc from cobalt in aqueous streams was achieved by successive stages of precipitation using lime. However, this technique was not able to meet the increasingly stringent metal quality requirements of customers whilst maintaining acceptable process recoveries. Intensive process development work was carried out and, in July 1988, an ion exchange circuit for nickel removal was commissioned using DOW XFS 4195 resin and for the first time Z.C.C.M. produced high purity cobalt metal containing less than 0.10% nickel. Following further work, a solvent extraction circuit for zinc removal, using DZEHPA, was commissioned in February 1991 in order to enhance cobalt recovery by reducing co-precipitated cobalt losses. This paper outlines the process development, design, commissioning and subsequent operation of these nickel ion exchange and zinc solvent extraction circuits.

Jan 1, 1993

By Christoph Zschiesche

Managing complex material streams within a lead smelting/reduction process has a long history at Aurubis. After modernization of the secondary lead smelter in 1991, Aurubis operates an electric furnace and a Peirce Smith converter to process complex secondary materials. This process links the copper and the lead metallurgy allowing Aurubis to properly combine primary and secondary process lines to optimize the processing of complex raw materials and smelter intermediates. However, combination of copper and lead metallurgy processing requires a continuous evaluation as raw material quality and composition varies. This paper describes Aurubis lead smelter processing and provides some fundamental considerations to optimize the lead processing, in particular with aspects related to speiss formation