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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 J. P. Bellot

During the non-ferrous metal processing, the melting step under vacuum or under rarefied gas leads to volatile metal losses. It is the case of the metallurgical processing of the nickel-based, titanium-based or zirconium-based alloys where the evaporation losses don't allow a sufficient control of the alloy chemical composition. A theoretical approach has been carried out involving both a continuum description in the liquid phase and a molecular approach in the rarefied gas phase. The finite volume method is used in order to solve the coupled transport equationsin the liquid, whereas the Boltzmann equation is modelled by using a Monte Carlo method. At the liquid metal and metallic vapor interface, the volatilization and recondensation fluxes link up the two calculations. Simulation results are given for the melting and refining of reactive metals such as titanium alloys where the control of the chemical composition remains a major difficulty. The validity of the kinetic Langmuir's law is discussed for different operating conditions.

Jan 1, 1996

By F. A. Myzenkov

The technology developed by the authors uses new methods for raw material smelting in electric furnaces, a new autogenous method and apparatus for subliming smelting for antimony trioxide production and separation of antimony and gold. Concentrate produced from the ore deposits in Yakutia has the following average contents of main constituents, % by weight: 29.4 Sb, 1.2 Fe, 13.1 S, 40.0 SiO2, 0.2 As, 2.6 CaO and 45 g/t of Au. Unlike the technology used abroad a new autogenous method makes it possible to increase considerably specific capacity and reduce gold losses with antimony trioxide by several times. At the same time mineralogical composition of trioxide has improved considerably ? it has mainly a cubic base with prevalence of senarmontite. The content of a main component (Sb2O3) in the final product has increased from 99.0% up to 99.6% which means better quality and makes it suitable for use in special technologies. Despite a lower antimony content of the concentrate (29.4% as compared with over 33% as common in the world practice), an antimony recovery of 85.3% into a commercial-grade product has been achieved, as well as a gold recovery of 96.65% into a gold-antimony alloy. The technology for processing gold-antimony materials developed and introduced at the Ryaztsvetmet plant is unique in the world with respect to gold recoveries.

Jan 1, 2006

By R. Leiby

Prior to March 1992, the only component of the lead acid battery that was not recycled by East Penn Manufacturing Company was the sulfuric acid electrolyte. This acid was unusable in new batteries because the iron level was found to exceed new product specifications. The development of a liquid ion exchange process to remove the iron from the acid allows East Penn to currently recover over three million gallons of sulfuric acid annually. The process is based upon the use of an iron selective liquid ion exchange material or solvent to extract iron from the sulfuric acid electrolyte followed by regeneration of the solvent. Equilibrium and kinetic data for the extraction and regeneration steps were collected in order to scale up the process to commercial scale. An electrochemical process for the treatment of the acid used in the regeneration step was, also developed which significantly reduces the volume of strip acid required in the process.

Jan 1, 1995

By Farhang Hedjazi

Anglo Asian Mining have recently installed an industrial-scale UF/RO plant to treat process liquors from the integrated heap leach/agitation leach/ resin-in-pulp gold ore treatment facilities at their Gedabek gold-copper mine in Azerbaijan. The UF/RO plant is designed to treat 60 m3/h of leach solution to produce discharge quality water. The RO concentrate, which contains elevated concentrations of copper, silver and cyanide, is sent to the company’s SART plant for the recovery of the metal values as a precipitated sulphide concentrate and the cyanide, which is recycled to leaching. The new water treatment plant improves the sustainability of the operations at Gedabek by enabling replacement of fresh water input with RO permeate and safe discharge of permeate to the environment, during periods of excess water balance. The paper includes pilot plant data and early results from the full-scale plant.

By C. Pichler, A. Ressler, D. Gregurek, A. Spanring

In order to improve the refractory lining life at one of the RHI key customer test procedures were developed within a two years collaboration project. In the first year of cooperation detailed refractory corrosion work in the rotary kiln with Ca-ferritic slag was performed. The main results of the second year of cooperation, reported in this article, involve a detailed testing work with nickel matte and pre-selected refractory brands which was performed in TBRC. A first part of this work was a complete chemical and mineralogical characterization as well as FactSage calculations carried out on provided matte samples. According to these results testing in the TBRC was realized at different process temperatures with several magnesia-chromite bricks. Based on the mineralogical investigation a high chemothermal load caused by sulfidic matte resulted in a deep reaching infiltration of the brick microstructure and partly corrosion of main brick components.

Jan 1, 2015

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 Xirneng Zhu

The electrochemical behavior of Pittsburgh and Illinois coal pyrite in basic and neutral borate/sulfate solutions was investigated. In the transpassive region, aggressive oxidation of pyrite occurred. The reaction products in this region were Fe(III) oxide, sulfate ion and partially oxidized sulfur intermediates. The formation of sulfur and polysulfides was identified by in-situ Raman spectroscopy. The growth kinetics of the reaction product film, resulting from transpassive oxidation of coal pyrites, were studied using chronoamperometry measurement with both stationary and rotating disk electrodes. The reaction rate was well correlated by a paralinear rate equation. The effects of electrode rotation speed, solution pH and temperature were examined. The kinetics were compared to those for mineral pyrite.

Jan 1, 1994

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 Ángel Ruiz-Sánchez

Ethylene glycol additions to aqueous acid solutions for leaching copper sulfides increase both copper and iron extractions compared to a conventional sulfuric acid leach with hydrogen peroxide (H2O2). The role of ethylene glycol is to prevent peroxide destruction, which normally occurs in solutions that contain both cupric and ferric ions. However, despite this improvement, ethylene glycol and sulfuric acid concentrations must be high (3.5 M and 0.7 M, respectively) to obtain satisfactory conversion levels at room temperature. In the present investigation, EDTA was used as an additive to complex the cupric and ferrous ions, lowering the requirements of ethylene glycol and H2SO4 to 0.11 M and 0.007 M, respectively, while minimizing oxidant decomposition. The experimental results for a mainly chalcopyrite, copper concentrate showed complete copper extraction in 24 h at room temperature, with the stoichiometric quantity of EDTA for the copper and iron dissolved. Tests using seawater were equally as successful.

By N. Kanari

Reactivity of MgO towards C12+air, C12+N2 and C12+CO gas mixtures was studied up to 1000 °C. Carbochlorination of MgO occurs at temperatures lower than that of its oxychlorination. Effects of gas flow rate, temperature and partial pressure of the carbochlorinating gas mixture on the reaction rate were investigated. The apparent activation energy of MgO carbochlorination is 49 kJ1 mol between 425°C and 600°C. At 550 °C, the apparent reaction orders with respect to C12+CO, C12 and CO, are 2.37, 1.47 and 0.89, respectively. At this temperature, the maximum reaction rate was obtained using a C12+CO gas mixture having a Cl2lCO molar ratio equal to about 0.6.

Jan 1, 1998

By J. S. Kirkaldy

A theoretical procedure is demonstrated for calculating two-dimensional binary cellular single-valued interfaces and extended to triple-valued (remelt) shapes. The numerical calculations for the single-valued local equilibrium problem which yield unique shapes as functions of the supersaturation parameter a and the partition coefficient k are reviewed. The cell amplitude L and wavelength A scale identically as the inverse velocity to the 112 power and the aspect ratio r is a constant equal to 312, independently of a and k for a < 0.5.. For 0.5 < a < m, L, A and r decrease asymptotically to zero indicating the finite amplitude nature of the instability at a = 1 and the existence of sub-marginal states which converge to a flat interface at a- m (Glv- m). Scaling comparisons between equilibrium single-valued and triple-valued and deep-rooted non- equilibrium cells are made.

Jan 1, 1992

By Z. R. Llanos

This paper presents a review of industrial and experimental processes for the recovery of molybdenum, vanadium, nickel, cobalt and aluminum from spent hydrotreating or hydrodesulfurization catalysts. Numerous processes have been developed in a laboratory and pilot scale. However, worldwide, there are only four well established commercial facilities currently in operation. The installed capacity of these facilities exceeds the availability of spent catalysts and may be sufficient to assimilate future increases of spent catalysts. Despite liability risks; significant quantities of spent catalysts are still being landfilled. Changing regulations that may affect the future handling and disposal of spent catalysts are also reviewed.

Jan 1, 1995

By Stephen Northey, Nawshad Haque, Terry Norgate

"Life cycle assessment (LCA) is a recognized tool to evaluate various processing routes for metal production. Declining ore grades and higher specific energy requirements for primary metal production put greater emphasis on recycling. Greenhouse gas (GHG) emissions of steel and aluminium metal production were quantified with recycling scenarios using material recovery facility (MRF) data from the database of SimaPro LCA software. The GHG footprint of the MRF is relatively minor compared with that of associated transport during collection (i.e. 10 times more than MRF) of curbside recyclable material. Additionally, if the bulk recyclable material is sent overseas (i.e. Australia to China) from the MRF for further processing, the GHG footprint of shipping can significantly be larger compared with the sum of the collection and MRF (assuming electricity is from same source). Thus opportunities exist for reducing GHG emissions from secondary metal production if it is processed close to the MRF.IntroductionIt is a challenge to recycle metals significantly, although theoretically infinite recycling is possible due to their elemental nature. Leaks from the metal stocks in society occur through corrosion, wear and dispersive uses, or via land filling or similar activities that return metals to the earth. In order to provide a technically sound and transparent assessment of metal recycling, a methodology such as life cycle assessment (LCA) should be used. By taking a life cycle perspective, the beneficial recycling properties of metals can be evaluated in a manner that enables appropriate comparisons with other materials or product systems that do not have recycling loops. In practice, mixtures of primary and secondary metals are often used in new products, and also at the end-of-life various processing methods are used for recycling.The difficulty of introducing recycling into LCA is to set the right boundaries for the different flows ending in different product systems. It is a question of which observed material flow belongs to the first product system and which one to the second or subsequent systems. Recycling can be part of any product LCA. However, it is often a complex issue which requires specific considerations. As pointed out by Yellishetty et al. and Birat et al. [l, 2], LCA practitioners are left with much freedom in allocation of environmental burdens to account for recycling, thus making subjective judgments on recycling and allocation of credits to recycling. This often makes it difficult to compare the results of LCA studies conducted by two different practitioners even on the same processes. As LCA is often used to define policy in government, business and society circles, it should be based on a sound, objective and unbiased description of recycling."

Jan 1, 2014

By T. K. Mukherjee, C. K. Gupta

"The importance of the processing of secondary resources such as solid industrial wastes and liquid effluents as well as byroducts for the recovery of the associated metal values hardly needs any elaboration. Such processing contributes in no small measure towards the augmentation of the availability and the supply position of resources. As an added benefit, it leads to a reduction in environmental pollution caused by the undesirable waste materials. As some typical examples of secondary resources in the Indian scenario, mention can be made of spent catalysts, metal/alloy scrap, ash, consumed batteries, flue dust, slag, sludge and slime, pickling solutions, spent acids, plating rinse solutions, spent etchants, waste water from synthetic fibre manufacture and from tanneries etc .. These wastes constitute a source of a variety of non ferrous metals. In the processing of secondary resources like these, the techniques of hydrometallurgy such as solvent extraction playa pivotal role.This paper outlines the efforts made to use solvent extraction to recover (1) base metals such as copper, zinc, nickel and cobalt from a number of secondary resources like cake, and sludge (2) refractory metals like molybdenum and vanadium from sulphidic byproducts and spent catalyst and (3) nuclear metal like uranium from phosphoric acid. In the case of base metals, process flowsheet involving the use of acidic extractants such as DEHPA and PC88A have been optimised. The problem of iron removal from the leach liquor, which influences the metal recovery process significantly, has drawn a special emphasis. In the case of refractory metals, basic extractants like Alarnine 336 has been pressed into service to produce kilogramme quantities of pure salts of molybdenum and vanadium. Finally, the paper gives a brief account of plant experience in recovering uranium from phosphoric acid, using a solvent system comosed of DEHPA and TOPO."

Jan 1, 1996

By Kandipati Sreenivasarao

Ion and precipitate flotation involve adding an appropriate collector to aqueous solutions containing metal ions, to form hydrophobic metal-collector complexes or precipitates that can be removed by flotation. With a better fundamental understanding of the effects of physical, engineering and chemical parameters on the performance, ion and precipitate flotation techniques could usefully complement techniques now available for removing metal ions from dilute solutions. The removal of Cu(II), Pb(II), Cd(II), Cr(III) and Cr(V1) has been studied, using different types of collector, according to the nature of the metal-bearing species. The effects of collector/metal ion ratio, and solution and froth height on the flotation kinetics, bubble coverage by the metal-collector complex, recovery of metal and effluent quality are reported. The observed behavior is related to the solubility products of the metal-collector complexes, which were also determined.

Jan 1, 1994

By R. J. Kuczynski

The U.S. Bureau of Mines Reno Research Center operated a batch pilot plant to demonstrate high-temperature cyanide leaching for recovering platinum group metals (PGM) from automobile catalysts. Approximately 1,600 kg of used pellet, monolith, and metal support catalyst containing 1,680 g (54 tr oz) of PGM were processed. Forty-five-kilogram batches of used catalyst were leached with sodium cyanide solution at 160° C for 1 h under basic conditions in a countercurrent processing sequence to dissolve the PGM. Extractions from the used pellet catalyst ranged from 94 to 95 pct for Pd, 95 to 97 pct for Pt, and 64 to 81 pct for Rh. Extractions from the used monolith catalyst ranged from 7B to BB pct for Pd, 75 to 90 pct for Pt, and 43 to 71 pct for Rh. Heating the pregnant leach solutions to 275&apos; C for 4 h destroyed the PGM-cyanide complexes, resulting in over 99.7 pct of the PGM precipitating from solution. The PGM precipitate was predominantly a powder metallic concentrate, typically analyzing greater than 50 pct PGM. Heating destroyed cyanide to less than 0.2 mg/L. Both the pellet and monolith residues were evaluated for disposal using the EPA Toxicity Characteristic Leaching Procedure.

Jan 1, 1995

By D. Y. Wang, G. Y. Sha, X. L. Shen, D. R. Gu

The study of the volatilization kinetics of zinc and lead in pellets made of zinc-leadbearing dust mixed with coal powder, in a nitrogen atmosphere and at a temperature range between 1100 °C and 1300 °C, shows that the reduction temperature has a significant effect on the volatilization rates of zinc and lead, and that both the particle size of the coal powder and the extra carbon content has no effect on the volatilization rates. The obtained activation energies for the volatilization of zinc and lead are 79.42kJ/mol and 88.74kJ/mol respectively. The volatilization rate of zinc is controlled by the reaction between the zinc oxide and carbon monoxide while that of lead is controlled by the lead evaporation reaction, and the diffusion of gaseous lead through the gas boundary layer covering the surface of the reduced liquid lead.

Jan 1, 2000

By Milton Blander

A review of concepts and theories for predicting thermodynamic solution properties of multi- component high temperature liquid solutions is reviewed. During the last 50 years the ability to predict :such properties for molten salts, silicates and metals based on the generally known properties of the lower order (often binary) systems has been developed and shown to provide predictions which are quite useful in science and technology. There are many gaps in our understanding of these high temperature solutions, especially for metals, and considerably more work is needed.

Jan 1, 1996

By T. K. Mukherjee

The importance of the processing of secondary resources such as solid industrial wastes and liquid effuents as well as byroducts for the recovery of the associated metal values hardly needs any elaboration. Such processing contributes in no small measure.towards the augmentation of the availability and the supply position of resources. As an added benefit, it leads to a reduction in environmental pollution caused by the undesirable waste materials. As some typical examples of secondary resources in the Indian scenario, mention&apos; can be made of spent catalysts, metal/alloy scrap, ash, consumed batteries, flue dust, slag, sludge and slime, pickling solutions, spent acids; plating rinse solutions, spent etchants, waste water from synthetic fibre manufacture and from tanneries etc. These wastes constitute a source of a variety of non ferrous metals. In the processing of secondary resources like these, the techniques of hydrometallurgy such as solvent extraction play a pivotal role. This paper outlines the efforts made to use solvent extraction to recover (1) base metals such as copper, zinc, nickel and cobalt from a number of secondary resources like cake, and sludge(2) refractory metals like molybdenum and vanadium from sulphidic, byproducts and spent catalyst and (3:) nuclear metal like uranium from phosphoric acid. In the case of base metals, process flowsheet involving the use of acidic extractants such as DEHPA and PC88A have been optimised. The problem of iron removal from the leach liquor, "which influences the metal recovery process significantly, has drawn a special emphasis. hi the case of refractory metals, basic extractants .like Alamine 336 has been pressed into service to produce kilogramme. quantities of pure salts of molybdenum and vanadium, Finally, the paper gives a brief account of plant experience in recovering uranium from phosphoric acid, using &apos;a solvent system comosed of DEHPA and TOPO.

Jan 1, 1996