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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 C. Liliane Carvalho

In the current study, bio-oxidation tests were carried out in shaking flasks with a flotation concentrate containing the sulphides pyrite, arsenopyrite and gudmidite. The tests were performed with mesophilic microorganisms (At. ferrooxidans) at 30 °C and also with the moderate thermophile S. thermosulfidooxidans, at 50 °C. The effects of (i) previous adaptation of the microorganisms to the concentrate, (ii) ferrous iron concentration and (iii) pulp density (2%, 4% and 6% (w/v)) on the dissolution of the sulphide were studied through arsenic extractions. S. thermosulfidooxidans was more sensitive to the pulp density in comparison to At. ferrooxidans as a reduction in sulphide oxidation was observed with the increase in the solid content to 6%. Therefore, the mesophilic strain was selected for further work, which comprised a rolling bottle experiment at 10% solids. After 40 days of bio-oxidation, the solid material was subjected to cyanidation, which revealed 85% gold extraction as compared to 21% from the original concentrate. The antimony sulphide grains in the bio-oxidized product showed similarity to what was observed in the original sample, suggesting such particles were not susceptible to the bio-oxidation process.

By Jussi Vaamol

A commercial CFD-code was used to solve isothermal flow fields of gas and liquid in a Peirce-Smith converter. The model was validated with a 1/4 scale water model, and parametric study. Limits of the modeling technique used were recognized, but calculated results indicate that the present model predicts the general flow field with reasonable accuracy. The model was used to examine general flow conditions in an industrial scale PS-converter. Typical scaling factors of physical models were also evaluated with the aid of predicted bubble distribution, patterns of the flow fields and magnitude of flow velocities. The numerical simulations were found to open new viewpoints to the fluid dynamic related phenomena in the PS-process.

Jan 1, 1998

By L. Xia

Sodium silicate(s), also known as “water glass”, are one of the oldest and most widely used industrial chemicals. Its first use in Canadian operations can be traced back to around 1925, which coincided with early use of xanthates in mineral flotation. Silicate functions as a sulphide and non-sulphide gangue mineral dispersant, depressant and modifying reagent in grinding and flotation operations. It is believed that soluble sodium silicate promotes selectivity of value added sulphides against gangue minerals, resulting in both grade and recovery improvement. This paper seeks to link improved grade/recovery to the interaction characteristics of minerals and the sodium silicate. A systematic study was performed with individual mineral species, an artificially designed model ore and the feed ore from a copper flotation operation. The function of sodium silicate was evaluated in the context of colloidal chemistry and linked to mineral surface chemistry. Measurement of pulp rheology and mineral zeta potential identified that sodium silicate works as a dispersant. The dispersion is accomplished by increasing a mineral’s net surface charge, resulting in a change in slurry viscosity. Bench scale laboratory flotation tests suggest that better dispersion leads to a diminished interaction of chalcopyrite with gangue. The improved Cu grade and recovery then are likely in response to an increased accessibility to collector along with a linked increase in particle bubble attachment resulting in better separation efficiency. ToF-SIMS surface chemical analysis of the flotation samples found a higher proportion of sodium silicate on minerals from the flotation tailings relative to the concentrates. Moreover, attachment of sodium silicate appears to be mineral specific; the data indicates that sodium silicate favours the surface of gangue phases over the value sulphides.

By M. Wallin

Millions of tons of sludge from different metallurgical processes are produced worldwide annually, and the environmental impact of landfilling these often hazardous sludges stresses the need to understand their role as valuable resources. The current work explores the potential of producing a saleable low-phosphorous ferromanganese alloy by utilizing sludge from the silicomanganese industry together with an iron source. The aim of the project is to explore the feasibility and practical challenges related to reduction and dissolution of manganese and silicon from the sludge to liquid metal and slag. Parameters such as ratio of input material as well as the effect of adding limestone and coke to the mixture were explored by thermodynamic calculations and adapted experimentally. Results show that a ferromanganese alloy, in fact, can be formed, while silicon and calcium forms a complex slag that captures a significant amount of impurities.

By Ker-Chang Hsieh

Four three-phase equilibria and one two-phase equilibrium in the FeNi- S-0 quaternary system in the vicinity of 1023 K and Pso2 = 1 atm were studied using the following emf cell 2 Pt,o2 (air)Zr02 .CaO/Pso2 = 1 atm, mixture of phases, Au The four three-phase equilibria are sp + (Fe,Ni )S + Ni 3s2, sp + Ni 3s2 + NiO, sp + NiO + N1S04 and Fe2 o3 + sp + (Fe,NOS04 -Y:he two-phase equilibrium is sp + (Fe,Ni)S. The two-.phase equilibrium was measured by using mixtures containing a major portion of one phase and a minor portion of the other. The results are presented in terms of oxygen potential as a function of YNi = nNi/(nN1+nFe) at constant temperature and pso2 = 1 atm. The stability diagram was also calculated using appropriate thermodynamic models for all the pertinent phases. The calculated diagram is in accord with the measured ones.

Jan 1, 1985

By A. M. Strachan

Capper Pass & Son Limited Was, until its recent closure, the world's largest producer of tin from secondary materials including solder drosses, non-ferrous smelter flue dusts, tin based metal alloys, residues and slags. Polonium-210, an alpha emitting radionuclide, was present in varying concentrations in some of the numerous feed materials processed by the smelter and refiner. The polonium-210 followed a complex path through the process flowsheet. This paper discusses the behaviour of polonium, both from its arisings in other smelters' process streams and through the entire Capper Pass smelting and refining circuit. The consequential personnel safety and environmental precautions necessarily taken in some areas of the process operation are outlined.

Jan 1, 1992

By G. Coryell, S. Blaskovich

"A computer model has been developed to simulate the flash furnace and converter operations at the ASARCO Hayden Copper Smelter. The focus of the modeling was to optimize the converter operation to eliminate high matte level episodes in the flash furnace. These episodes (reducing feed to the furnace) resulted from the lack of converter operation scheduling. The model provided ""what if?"" scheduling scenarios that led to increased efficiency of the converter and flash furnace operations.This paper discusses alternatives studied to optimize the converter operation and the development of the computer modeling program, including implementation of the project. The discussion details the results of the project including the conversion from batch to a real time converter scheduling process. IntroductionASARCO's Hayden Smelter consists of a fluid bed drying system, an Inco oxygen flash smelting furnace, Peirce Smith converters, two anode furnaces and two casting wheels, gas cleaning plant, 2800 stpd sulfuric acid plant, 650 stpd oxygen plant and 200 gpm water treatment plant. The process flow sheet of the plant is shown in Figure 1.Over the past several years, the Hayden smelter has been involved in productivity improvement and cost reduction programs. This has been necessary to become a low cost copper producer in today's market. Part of the productivity improvement program was the use of process control to streamline the flash furnace and converter operations. Process control, through the use of computers and electronic controllers, has played an increasingly important role in optimizing processes in the Hayden Plant since the startup of the Inco flash furnace in 1983."

Jan 1, 1989

By M. E. Huckman

In this paper, we review the equations needed to construct an ion exchange column model. These models contain three major components: 1) a differential material balance around the colunm, 2) a differential material balance around an ion exchange particle, and 3) a constitutive equation for diffusive flux We then examine the ability of a fairly simple mathematical model to predict ion exchange column experimental data. This model contains the traditional absorption theory equations and is used to predict the behavior of a column filled with a hydrous crystalline silico-titanate and which is removing trace amounts of Cs+ from a high pH, complex electrolyte solution. Finally, we propose replacing Fick's law with the Nernst-Planck equation as the constitutive equation for diffusive flux We use a Nernst-Planck type model to predict batch experimental data, then evaluate it by comparing it's ability to predict experimental data to that of a more traditional Fick's law type model? The data from this comparison suggests that the Nemst-Planck type model yields better results.

Jan 1, 1996

By Vaughan R. Voller

"Over the last ten years an increasing number of heat and mass transfer models of solidification processes have been presented in the literature. A key component in these models is the coupling between thermal and solute fields. This is achieved by developing relationships based on the behavior at the microscopic scale in the casting (typically a secondary dendrite arm space). An important class of models in this respect are models that describe the local scale redistribution of solute alloy components-collectively referred to as microsegregation models. This paper explores this class of models.IntroductionModeling takes a key role in processing materials for properties. This is particularly time in solidification processes where current computer techniques allow for a detailed treatment of the critical macroscopic phenomena. Typically these macro scale models consist ·of three main coupled components.1. A model of flow in the melt and solid + liquid mushy region.2. A model of heat transfer.3. A model of solute transport.The focus of this paper is the solute transport component, in particular the manner in which process scale transport is coupled to transport ·at the local scale of the solid-liquid interface. This step requires a modeling of the redistribution of solutes at the scale of the secondary arm spaces in the dendritic mushy region-a process referred to as microsegregation. Basic microsegregation models use the limit assumptions of no mass diffusion in the solid (Gulliver-Scheil [l]) or complete diffusion in the solid (equilibrium lever rule) in a fixed and space. Recently, however, more sophisticated microsegregation models that account for finite mass diffusion and coarsening of the arm space have been developed [2-19]. In this paper governing equations for a general microsegregation model for a multi-component alloy in a coarsening and spacing _are introduced. From these general equations various models for a binary system are developed and tested"

Jan 1, 2000

Proposed by outstanding electrochemist and electrometallurgist Prof. Raphael Agladze (191 1- 1989), process of copper and manganese co-electrowinning was enhanced to the pre- electrowinning stages: low,temperature co-leaching of copper and manganese containing materials, and to high-temperature co-roasting of the same materials with consecutive leaching. The report presents results of experimental investigations of the processes mentioned above, as well as results of thermodynamic investigations of co-roasting processes, and co- leaching processes computer modeling.

Jan 1, 1997

By Mingming Zhang, Marshall S. Coe, Marcelo W. Andrade

To supply iron units and flux burden in blast furnaces, sinter basicity is one of the vital parameters for sinter plants. The sinter basicity also plays an important role in sinter quality since it imparts the formation of different mineral phases in sinter. Pot-grate sintering tests were carried out with low and high basicity to investigate the effects of sinter basicity on sinter mineralogy, properties and productivity. It was found that with an increase in sinter basicity, both sinter productivity and reducibility (RI) increased. Tumbler index (TI) and low temperature degradation index (LTD) of high basicity sinter were comparable to low basicity sinter. Softening and melting tests showed that sinter with 3.5 C/S basicity had slightly higher softening temperature comparing to lower basicity sinter with C/S 2.6, acid and fluxed pellets. XRD analyses confirmed the formation of silico-ferrite of calcium and alumina (SFCA) and calcium ferrite (CF) in the tested sinter samples.

Jan 1, 2015

By Carl C. Nesbitt

A process has been developed to recover and recycle metals from wastes of brass foundries which contain copper, zinc and lead in various quantities. Tests were conducted to evaluate several leachants, including sulfuric acid, ammonia, hydrochloric acid, cyanide and acetic acid, and to determine the optimum leaching conditions, such as air flow rate, initial copper ion concentration, temperature, and agitation strength. Sulfuric acid containing copper sulfate with dissolved oxygen is the most successful leachant. More than 99% of the copper and zinc originally present in the waste was dissolved, while only 0.5% of the lead entered the solution after 14 hours of leaching. The leaching mechanisms of copper, zinc, and lead are proposed. The copper and zinc can be recovered from the solution by electrolytic processing. The unleached residue may be converted to a lead carbonate which can be converted to litharge at 400-450°C and to massicot at temperature above 500°C by calcination.

Jan 1, 1995

By E. Bélisle, Christopher W. Bale, S. Petersen, C. Robelin, K. Hack, J. Melançon, G. Eriksson, A. D. Pelton, P. Chartrand, S. A. Decterov, I. H. Jung, A. Gheribi

The FactSage® package consists of a series of information, database and calculation modules that enable one to access pure substances and solution databases and perform thermochemical equilibrium calculations. FactSage was originally founded by process pyrometallurgists and has since expanded its applications to include hydrometallurgy, electrometallurgy, corrosion, glass technology, combustion, ceramics, geology, environmental studies, etc. With the various modules one can perform a wide variety of thermochemical calculations and generate tables and graphs of complex chemical equilibria and phase diagrams for multicomponent systems. This paper presents examples of recent and current developments in FactSage in areas of particular interest to Dr. David Robertson. These include both ferrous and non-ferrous processing, as well as solidification and refining simulation. The paper also includes reference to the Internet Fact-Web education package.

Jan 1, 2014

By C. Hennesmann, D. Maijer, S. L. Cockcroft, P. Yo

"Die cast aluminum wheels are one of the most difficult automotive castings to produce because of stringent cast surface and internal quality requirements. As part of a collaborative research agreement between researchers at the University of British Columbia and Canadian Auto Parts Toyota Incorporated, work has been underway to predict heat transport and porosity formation in die cast A356 wheels. The basic heat transfer equations have been solved using the commercial finite element package ABAQUS to which specialized routines have been added to predict porosity. Preliminary work on predicting porosity formation focused on using the Niyama parameter as a measure of the probability of porosity. The latest version of the model incorporates a new fundamentally based porosity criterion, which takes into account the effect of hydrogen concentration. The development of this model together with its application to a series of cylindrical test castings as well as a production cast wheel are presented.I. IntroductionDie cast aluminum wheels are one of the most difficult automotive castings to produce because of stringent cast surface and internal quality requirements. Microporosity, in particular, is a common defect that can adversely affect wheel quality. The mechanism of microporosity formation in aluminum alloys is complex owing to its dependence on the interaction of a number of phenomena occurring during solidification including the decrease in hydrogen solubility, the decrease in volume, the development of the solidification structure, and the increase in difficulty in interdendritic feeding [1]. As a result, the amount, size, and distribution of microporosity is affected by a large number of casting parameters including thermal variables, melt composition, grain structure, modification, and inclusion content, making optimization by trial-and-error methodologies difficult.The use of criteria functions, based on thermal conditions during casting, offers a relatively simple approach to predicting microporosity. In practical terms, they are useful because they provide a straightforward method of assessing the impact of varying casting parameters on porosity through various thermal parametersl21 such as thermal gradient, cooling rate, solidification time, and solidus velocity. Drawbacks of criteria functions include insensitivity to varying hydrogen concentration and the limitation to qualitative predictions. Consequently, in aluminum alloys, attempts have been made to develop models incorporating the effects of hydrogen gas and microstructure evolution. However, these types of models represent a significant increase in complexity and sacrifice the simplicity and ease of application of the thermally based criteria functions."

Jan 1, 2001

By T. R. A. Davey

A simple model for metal solution behaviour may be derived, on the basis of dilute solution solubilities (where? log concentration of solute varies linearly with reciprocal temperature) and not-so-dilute region solubilities (where the log of the alpha-function at saturation frequently varies linearly with reciprocal temperature) and assuming activity to vary according to the quadratic formalism in between. Matte binary systems usually exhibit regular .solution behaviour when the constituent species are chosen appropriately. In many recent papers, metal solubilities in .slags are expressed as the sum of several different and supposedly independant molecular species (e.g. oxides, sulfides, chlorides), Such a view is untenable because of the now proven ionic nature of slags. Some possible reasons for the great effect of sulfur on copper solubilities in slags are discussed.

Jan 1, 1985

By Donna M. Noel

Bacterial strains have been cultivated from solids previously exposed to cyanide that will tolerate 300 ppm sodium cyanide under anaerobic conditions. In selected solid samples, these bacteria have been shown to reduce the level of cyanide from approximately 300 ppm to essentially zero in about 50 days under anaerobic conditions. Various media were investigated, and the nutrients providing maximal growth were ?established .. Degradation of cyanide in sterilized solids was determined for comparison with degradation obtained in bioactive solids. All experiments were conducted at ambient temperature and initial pH of approximately 10.5.

Jan 1, 1991

By Gerardo Fuentes

The stoichiometry and kinetics of the hydrothermal reaction of enargite in copper sulphate solutions was investigated in the range 140–300 °C, and particle size under 15 and 50 μm. The stoichiometric experiment was performed at 300 °C, using one gram of sample (96% enargite, 4% tennantite) and 100 mL of copper sulphate solution (10 gpl) at 1.2 pH. Enargite reacted completely after 80 min. A solid product was obtained and characterized by XRD. The main product was chalcocite (M) and some traces of djurleite and chalcocite (Q). Tennantite did not react under these conditions. The kinetic experiments were conducted at 140 °C, 190 °C, 250 °C and 300 °C. From fitted data and Arrhenius equation the calculated activation energy (Ea) was 51 kJ/mol. According to the hydrothermal transformations studied, the reactivity of different phases found in the copper concentrates was bornite > chalcopyrite > covellite > sphalerite > pyrite > enargite > tennantite.

By J. Pesl, U. Kemey, F. Sauert

"The CONTOP® smelting cyclone is a water-cooled, upright, high-intensity smelting reactor. The technology for the reactor was initially developed and brought into industrial-scale operation in the area of non-ferrous metallurgy. The two largest smelting cyclones were built with a capacity of 32 tons per hour of copper concentrate mix.The newest industrial CONTOP® plant treats up to five tons per hour of zinc-bearing residues including EAF dust. The highly concentrated zinc-lead oxide produced is sold to the zinc industry. The slag fulfills the leaching criteria and is used in waterway construction. The heat transferred to the cyclone cooling system and the off-gas boiler produces steam from which power is generated in a turbine.V AI has erected a new CONTOP® demonstration plant at MEFOS, Lulea, Sweden. A zinc volatilization rate of 90% was achieved during hot commissioning with Swedish EAF dust.Treatment costs in the range of 85 to 100 EUR per ton were estimated in a feasibility study on the treatment of 73,000 and 57 ,000 tons EAF dust for a group of steelmaking mills in Southern Europe."

Jan 1, 2000

By Grégory Miette

The paper deals with a process that allows the recycling in a cupola of EAF dusts with 18 % Zn. It produces dusts with zinc grade higher than 50 - 55 % and commercial cast iron with less than 200 ppm Zn, 50 ppm Pb, 0.15 % S. The paper focuses mainly on lab tests made with the aim to develop an effective formulation of self reducing - melting pellets. With such a formulation, agglomerates develop a breaking load higher than 125 - 150 kg without any thermal treatment. Zinc and lead are volatilized in the cupola with yields higher than 95 % at 1200 OC, before any melting. Sulphur is transfemed into gas and slag. All these conditions allow to lower zinc, lead and sulphur grades below the cast iron specifications. Results of first bench scale tests performed at Fonderie Piret to validate the process will be presented.

Jan 1, 2002