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By L. R. Verney

About 75% of the market economy countries's supply of cobalt is produced in Central Africa by Zafre and Zambia. Zafre alone accounts for more than 55% and has the resources and capacity to increase output significantly at any time so its dominant position is unlikely to be challenged in the foreseeable future. Other producers from domestic resources are Canada, Australia and South Africa; and Cuba, probably the most important producer outside of the Market Economy countries. Belgium, Norway, France, Japan and Finland produce cobalt from imported materials. While there are "cobalt ores", inMorocco, USA, Canada and the USSR, the mineralisation is complex and cobalt extraction is costly. In ZaPre and Zambia cobalt is a by-product of copper; in Canada, Australia, France, and Cuba it is a by-product of nickel; and in South Africa it is a by-product from the production of Platinum Group Metals. Thus the levels of cobalt production are inevitably related to the production of other primary metals. While some cobalt is produced by predominantly pyrometallurgical methods most of the world's cobalt is produced hydrometallurgically. The existence of large hydro-electric power plants and the mineralogy of the copper and cobalt concentrates encouraged research and development in Zafre of the recovery of copper and cobalt by electrowinning from sulfate solutions; much pioneering work was carried out, which lead to construction of the two largest copperlcobalt hydrometallurgical plants in the world, at Shituru and Luilu. Similar systems were adopted in Zambia. In Canada high pressure hydrometallurgical processes based on the sulfate system were developed and adopted in Australia, the Philippines, Finland and South Africa. Meanwhile developments in chloride hydrometallurgical extraction of nickel and cobalt lead to its use in the extraction of cobalt in Norway, France and Japan.

Jan 1, 1988

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 N. Pradhan, B. K. Mishra, B. D. Nayak, B. K. Mohapatra, R. K. Mohapatra

"Present study is about use of a group of Iron[Fe(III)] Reducing Bacteria (IRB) to convert the goethite (a-FeOOH) present in the original lateritic Nickel ore to magnetite under an anaerobic condition and subsequently release the bound Co(III) and Ni(II) through leaching. The lateritic Nickel ore contains 0.8% Ni, 0.049% Co, 1.92% Cr, 0.32% Mn and 50.2% Fe. An anaerobic dissimilatory Fe(III) reducing bacterial consortium capable of using acetate as carbon source (electron donor) and lateritic ore as terminal electron acceptor, changes the initial light brown color of the ore to dark brown. The change in color is due to the conversion of goethite to magnetite, which was confirmed by XRD. When the IRB treated sample was subjected to both bioleaching and acid leaching, it shows a greater recovery of Nickel and Cobalt values as compared to untreated original lateritic Ni ore. Further a magnetic separation method was used to separate the magnetic part of the treated lateritic ore and subjected to acid- and bio-leaching for better recovery of Nickel and Cobalt.IntroductionIt has been known that micro-organisms have the potential to reduce metals but more recent observations have shown that a diversity of specialist bacteria and archaea can use such activities to conserve energy for growth under anaerobic conditions [12]. Natural Fe(III) oxides are high in surface area and are reactive [1]. Fe (III) oxides adsorb a wide range of metal cations and anions by complexation to surface hydroxyl groups [17], and function as the primary redox buffering solid phase in many sediments and subsurface materials [5].Recently a number of bacteria have been isolated based on their ability to use metal ions, including Fe(III), as electron acceptor under anaerobic conditions. These are capable of producing energy by coupling the oxidation of organic compounds to reduction of Fe(III). Iron[Fe(III)]-Reducing Bacteria (IRB) have been isolated and identified from a wide variety of environments including freshwater and marine aquatic sediments and submerged soil [8]. The biogeochemical cycle of iron is linked to those of the trace metals, as many trace metals coassociate with Fe(III) oxides or reduced iron phases (e.g., magnetite, siderite, or iron sulfide). IRB can utilize Fe(III) oxides as terminal electron acceptors for respiration [18]; thereby reducing all or a fraction of the solid. The reductive portion of the iron biogeochemical cycle in non-phototropic environments (e.g., sediments and subsurface materials) is driven by the direct enzymatic reduction of Fe(III) oxides to Fe(II) by dissimilatory iron reducing bacteria [13,14]."

Jan 1, 2009

By Mei Yang, Wei Gao, Jian Yang, Qingcai Liu, Wenchang Xi

"TiO2 has been loaded on cordierite porous ceramic to prepare the SCR catalyst carrier by using both APCVD and sol-gel technology. In APCVD method, TiC14 and O 2 were used as reaction precursor. TiC14 was gasified by using N2 as carrier gas which was controlled to 500sccm. Its reaction temperature and reaction time were limited to 773K and 30min respectively. The physical properties, SEM and SEM-EDX of the TiO2-cordierite carrier and the properties of SCR catalysts prepared by these carriers have been tested. The tests showed that TiO2 loaded by APCVD method were of graininess shape and even accumulation. The loading rate of TiO2 and the specific area of carrier sample were increased 114% and 21 % respectively comparing with sol-gel technology. In the result of sol-gel method, the maximal difference of Ti content was 66.92%, while the result of APCVD method was 18.89%. It demonstrated that TiO2 was uniformly attached with the cordierite ceramic by using APCVD method, which would ensure more active ingredients well loaded on the Ti02-cordierite carrier. This difference made the denitrification ratio of catalyst prepared by APCVD method was 8.1 % higher than that of catalyst prepared by sol-gel method.IntroductionIn recent years, the emission of NOx, which were caused by coal-fired power plants, has gotten more and more attention. SCR (selective catalytic reduction) is the most effective technology to DeNOx [ll. The core technology of it is the catalyst. The SCR catalyst usually uses Ti02 as the carrier, and V2O 5 as the active component [2, 3] . However, the thermal stability and mechanical properties of TiO2 carrier are unstable, which would influence the performances of the catalyst. The commercial catalyst generally uses WO3 or MoO3 to promote its heat stability at present [4-7] Besides, TiO2 is expensive. Compared with TiO2, the cordierite is of good thermal stability and lower price. So loading Ti02 on cordierite porous ceramic as carrier to produce SCR catalyst is of good prospects [S, 91 • Currently, TiO2 is usually loaded on cordierite by the sol-gel method. But some research has shown that the sol-gel method easily reduced the loading performances of TiO2, such as distribution, combination, etc. APCVD (atmospheric pressure chemical vapor deposition) has many advantages to preparing TiO2 films, such as high bonding strength, fast reaction rate and so on [l0-13l_ In this paper, TiO2 has been loaded on cordierite porous ceramic to prepare the SCR catalyst carrier by using both APCVD and sol-gel methods. The properties of the carriers prepared by the two processes have also been compared."

Jan 1, 2011

By Tian Sugui

By means of the long-term aging treated, creep properties measuring and microstructure observation, an investigation has been made into the microstructure and creep behavior of the casting and rolling GH4169 superalloy after long-term aged. Results show that, after the casting and rolling GH4169 superalloy treated by long-term aged, significant amount of " phase are dispersedly precipitated within the grains of the alloy, and some of the NbC, Cr7C3 carbide are distributed along the grain boundaries. In the range of the applied stresses and temperatures, the creep activation energies and stress exponents of LTA GH4169 alloy during steady state creep are calculated to be Q=541.1kJ/mol and n=16.2, respectively. During creep, the deformation mechanism of LTA GH4169 is thought to be the twinning and dislocation slipping within the twinning regions, and the damaging mode of the alloy is the intergranular fracture, and the non-smooth crystal surface is displayed in the fracture regions of the alloy. Thereinto, the carbides film formed along the grain boundaies has a few effect on the strength between the boundaries, which is a main reason of resulting in the alloy possessing a longer creep lifetimes.

Jan 1, 2009

By Bruce H. Baker

Studies of used or unused refractory materials are excellent examples of applied mineralogy in industry. Refractory materials are mineral substances containing ceramic or chemical bonding systems. Knowledge of the mineral composition, bonding, and textural relationships often explains the resulting physical property values of a refractory and contributes to the interpretation of refractory wear mechanisms occurring in steel plant service.

Jan 1, 1982

By Lawrence D. May, Harry Mudgett

"In the course of developing a new industrial process, information produced at the Research and Development (R&D) stage is critical to determining the technical and economic feasibility of the project. Understanding the fundamental operating parameters for each unit operation in a flowsheet typically comes from historical knowledge of similar systems or by technical development through a robust research program. This approach holds true for processes incorporating fluidized-bed technology. In this paper, the authors will present a practical approach for performing a research study that will allow a process owner to determine if the concept of using a fluidized-bed system can become a reality. Included are discussions of key steps required at each level of the R&D program, and the critical information required for advancing the project to the next stage.IntroductionThe conduct of a research and development program typically starts with a process owner identifying a new industrial need or modification to an existing operation. The owner can pursue this need through multiple routes, including initial in-house development, coordination through an engineering firm, contacting suppliers of key equipment envisioned for the process, or through direct contact with research and development organizations. Where and when the project is conducted is as variable as the number and types of owners who pursue them. Factors that can influence the decision of where to conduct a research program can include the type of process desired, the scale and scope of the project, the location of the project site relative to the R&D options, the experience, capability, and availability of the potential research sources, and the costs to conduct the program. Often, the owner may choose a combination of the available resources to achieve their objectives. In the end, the owner's choice should be based on a thorough understanding of their goals and objectives for the program, and a good understanding of how to measure success while achieving those objectives. Herein, the authors will describe the methods we have typically used to develop the information an owner needs to make an educated decision for investing in a new or modified process."

Jan 1, 2014

By Carlos Mauricio Fontes Vieira, Sergio Neves Monteiro, Thiago Samarão Motta

This work has as its objective to characterize ceramic bodies formulated with ornamental rock waste and two different clays to produce ceramic paver. Specimens were made by uniaxial press-molding at 20 MPa and then fired at 950 and 1050oC respectively. The determined technological properties were: plasticity, dry bulk density, linear shrinkage, water absorption and flexural rupture strength. The results showed that the type of the clay has strong influence on the properties of interest for heavy clay ceramics. The investigated waste must be incorporated in small amounts to avoid increasing in the porosity of the ceramics.

Jan 1, 2015

By Shun Myung Shin, Kang Jeong, Kyoungkeun Yoo, Jin Koo, Dong Hyo Yang, Soo Sohn

"The optimum discharging condition to dismantle the batteries without explosion was investigated to recycle the lithium primary batteries, which could be exploded by heating too much or crushing. The 3 waste lithium primary battery cells were discharged with 500 cm3 of 0.5 kmol·m-3 sulfuric acid. Fe concentration and pH increased rapidly after 3 days at 35? and after 1 day at 50?. Chromium concentration increased by 4 days at 35? and 2 day at 50?and then decreased, and nickel concentration was very low. Because Li concentration increased gradually, Li became dissolved after the dissolution of cover material. When the discharged batteries were shredded, the batteries discharged at 50°C were not exploded and those discharged during 3 days at 35°C were exploded. This result shows that the waste batteries could be stabilized within 1 day at 50°C and 4 days at 35°C. Introduction Lithium has some advantages for battery e.g. it is the lightest metals and also has the highest electrochemical potential at 3.04V[1]. For over thirty years lithium primary batteries became famous for their performance in various applications such as IT, medical, and military[2,3]. They gained a reputation for their long shelf life, constant voltage, wide operating temperature range, and low self-discharge characteristics[3-5]. World primary lithium battery market was expected to grow from $820.6 million in 2003 to $1,1355.3 million in 2010 (http://www.frost.com, Frost & Sullivan)[2-4]. The lithium primary batteries have very various sizes and components. Lithium batteries are made with lithium metal as anode active material and non-aqueous solvent as electrolyte. As cathode active material, various kinds of materials were used such as manganese dioxide (nominal voltage, 3.5V), thionyl chloride (3.6V), and carbon monofluoride (3.0V). In Korea, 50 % of the spent lithium primary batteries must be recycled because spent lithium primary batteries have been listed in EPR (Extended Producer Responsibility) of the enforcement degree of the act on the promotion of saving and recycling of resources. However, the batteries have been landfilled since there is no economic method to recycle the batteries in Korea[2,3]. When the batteries were heated too much, charged, pierced, over discharged, or short-circuited, the batteries explode because lithium reacts violently with water or air and because contents such as lithium, electrolyte, and sulfur become flammable by high temperature[4]. Therefore, it is so difficult to recycle safely the spent lithium primary batteries."

Jan 1, 2008

By L. Filip

The roast-leach-electrowinning (RLE) process for zinc was modified to treat two typical complex concentrates containing zinc, lead, copper, gold and silver. Laboratory testwork results indicated that the optimum roasting temperature ranged from 700 to 800°C, in order to produce acceptable residual sulfur levels. The calcined concentrate was subjected to a three-stage leach sequence. The resulting leach solution was purified by hematitic precipitation and directed to the recovery of copper and zinc by solvent extraction and electrolysis. Alkaline smelting and subsequent electrolytic purification recovered the lead and precious metals from the leach residue. A flowsheet was developed based on the laboratory testwork results, and demonstrated in a large-scale pilot plant. The recoveries produced during the pilot plant operation ranged from 90 to 92% for zinc and copper, 85% for lead and 90% for gold and silver, respectively.

Jan 1, 1999

By Susanne Pignolet-Brandom

QEM*SEM is an automated scanning electron microscope/computer system that characterizes samples with regard to mineral modal abundances, mineral grain and particle sizes, mineral associations, and particle surface areas. Additional information, based on the classification of particles according to the area percentage of a mineral of interest, can be obtained for samples of particulates. QEM*SEM is capable of analyzing a wide variety of materials although it was originally developed for applications to the minerals industry.

Jan 1, 1988

By W. Kunda

A laboratory study was carried out on the treatment of sulphidic copper concentrates in aqueous chloride systems under elevated temperatures and oxygen overpressure. Exploratory tests showed that chalcopyriteoxidizes with various chloride salts to form, depending upon the pH of the system, soluble copper chloride or insoluble copper oxychloride salts; the copper can then readily be recovered from the solution or residues respectively. During the leaching, iron was oxidized to iron oxide and remained in the leach residue while the bulk of the sulphide sulphur was oxidized to the elemental form with a minor portion oxidized further to sulphate. The presence of metal chloride salts in the system increased the oxidation rates of chalcopyrite and depressed the solubilization of iron in the system. A systematic oxidation leach study carried out in (1) ammonium chloride and (2) sodium chloride systems showed that the former system required little or no HC1 addition while the latter required 2 mol of HC1 per mol of dissolved copper (plus zinc). The copper was recovered from the cuprous or cupric chloride leach solutions by cementation with iron. Extractions of 99% copper and zinc, 97% silver, and negligible iron were obtained. Sulphur was oxidized to the elemental or sulphate form; the relative proportions of the total sulphur were 60 and 30% for system (1) and 80 and 10% for system (2). A flowsheet for a conceptual process with minimal reagent requirements was proposed.

Jan 1, 1976

By Xiaojian Zuo, Yihua Han, Qingguo Xue, Jingsong Wang, Lintao Wang, Rongzong Lan

"Using the facility of reduction experiment, the low temperature reduction pulverization and reduction behavior of sinter in oxygen blast furnace (OBF) were studied. Through analyzing the results, the difference of pulverization and reduction behavior of sinter in OBF and conventional blast furnace (BF) were discussed. Furthermore, the effect laws of reduction temperature and the content of CO and H2 on reduction behavior of sinter were studied. Also the controlling step of iron oxide reduction was discussed. Compared with BF, the low temperature reduction pulverization of sinter became serious at 773 K; reduction rate became faster at 1173 K; reduction time became less and final reduction degree was increased in OBF. With increasing of H2 and CO contents, the reduction of sinter was promoted. The reduction process was controlled by interface chemical reaction at the earlier stage and by interface chemical reaction and internal diffusion at the final stage.IntroductionThe new ironmaking technology of Oxygen Blast Furnace (OBF) is most likely to be used in large-scale application process. The concept relies on the removal of the CO2 contained in the top gas of the blast furnace. Therefore the useful components, i.e. CO+H2, can be recycled back into the furnace and reused as reducing agents. In addition, injecting oxygen (O2) into the furnace instead of preheated air, removes unwanted nitrogen (N2) from the gas. Under the pressure of CO2 emissions in iron and steel making, the growing international shortage of coking coal resources and the rising price of coke, OBF has attracted attentions of both domestic and foreign researchers, because it has so many advantages such as high productivity, high PCI rate, low coke rate, high gas reducing capability and high top gas calorific value, etc [1-7]. As a result of recycling most of the top gas after CO2 removal and injecting oxygen into the furnace, the reduction capacity of blast furnace gas will be increased, so the metallurgical behavior of OBF's iron burden is different from traditional blast furnace. Therefore, it is one of the keys to develop this technology, which studies the metallurgical behavior of sinter in OBF. The purpose of this paper is to study the low temperature reduction pulverization and reduction behavior of sinter at the atmosphere of OBF, which includes the difference of low temperature reduction pulverization and reduction behavior of sinter in oxygen blast furnace and conventional Blast Furnace (BF). It will provide theoretical basis for the development of OBF."

Jan 1, 2012

By Guiming Yang, Xiaoxian Huang, Zhiyun Ji, Min Gan, Lishun Yuan, Xiaohui Fan, Zhiyuan Yu

"The roasting characteristics of hematite pellets containing MgO were studied where magnesia powder, serpentine and magnesite were used as magnesium-additives respectively. The mechanical strength of both preheated and roasted pellets decreased when MgO content increased, which implied the addition of MgO had an adverse effect on pellet consolidation. By adding flux containing CaO, the mechanical strength of both preheated and roasted pellets were improved. The addition of calcium flux facilitated the formation of calcium ferrite and provided a certain amount of liquid phase, resulting in faster diffusion ofMg2+ and Fe3+. The result showed that diffusing speed of Mg2+ was enhanced by 1.48 times, and rate constant of Fe203 crystalline growth was enhanced by 62% when basicity was around 0.4. Improvement of mineralization degree and recrystallization of Fe203 assisted in consolidation of hematite pellets containing MgO.IntroductionOxidized pellets are ideal iron-bearing burdens in blast furnace. At present, magnetite is the main raw material for oxidized pellet production in China. However, as the rapid development of iron and steel industry, resources of magnetite have been depleted and cannot satisfy the requirement of pellet production. Using hematite concentrates to produce oxidized pellets has become a trend [1, 2]. Many pellet enterprises abroad nowadays have adopted high proportions of hematite concentrates when producing oxidized pellets, e.g. the percentage is 100% in a lot of Brazilian factories [3, 4]. But high proportion of hematite concentrates will lead to low mechanical strength and high reduction swelling index of pellets. Some studies show that Mg-bearing pellets have excellent metallurgical properties, and the reduction swelling phenomenon can be solved by adding fluxes containing MgO [5, 7]. However, there are problems such as low pellet strength and bad roasting characteristics for MgO-bearing pellets, which remains an obstacle in pellet industry. Hence, it's vital to undertake the study on strengthening measures for indurations of Mg-bearing hematite pellets."

Jan 1, 2013

By Daojin Cao

The chemical components in the saturated aqueous solution of ammonium dimolybdate (ADM) were investigated at room temperature by comparative Raman spectroscopy. In order to explore the further detailed results, a new method of qualitative and half quantitative analyses, based on the main vibrant frequencies and the intensity ratio of the strongest peak to the second strongest peak recorded in Raman spectrum of saturated aqueous solution of ammonium heptamolybdate tetra hydrate (AHM), was put forward and attempted to analyze the chemical components of saturated aqueous solution of ADM. The results showed that there was obvious difference between Raman spectrum of saturated aqueous solution of ADM and that of ADM, but there were good relationships between Raman spectrum of saturated aqueous solution of ADM and Raman spectra of the three samples including AHM, the saturated aqueous solution of AHM and monomolybdate ion in aqueous solution. It was found that aggregated dimolybdate ion ({Mo2O72-}n)did not exist in the saturated aqueous solution, and was changed into heptamolybdate ion (Mo7O246-) and monomolybdate ion (MoO42-), which were in equilibrium each other, but the distribution ratio of heptamolybdate ion was larger than that of monomolybdate ion. In addition, Raman spectral pattern of saturated aqueous solution of ADM was reported.

Jan 1, 2006

By Messias dos Santos Machado, Renato B. Godoy, Roberta Lima, Andressa Silva, Francisco Valenzuela-Díaz, Rene R. Oliveira, Esperidiana Moura

This work aims to incorporate the Bof White Clay, from Boa Vista, Paraiba State, Brazil, as natural nanofiller in Ehylene vinyl alcohol copolymer (EVOH) and obtain flexible films. Nanocomposite was obtained using a twin-screw extruder, and film formed using a blow extruder machine. The flexible film nanocomposite was characterized, by tensile tests, XRD, DSC and their properties were evaluated. The results showed a good interaction between the clay and the EVOH resulting in an increase of properties of films nanocomposites as compared to films neat polymer.

Jan 1, 2015

By Robert Fritzsch, Ragnhild E. Aune, Mark William Kennedy, Behzad Mirzaei

"The quantitative particle concentration can give important information about the cleanliness of melts for quality control in primary and secondary production of aluminum. Manual quantification of the particle concentration is normally a time consuming process and human control can bias the acquired images and particle count.The present paper explains the automated image-processing steps for the quantification of SiC-particles, with equivalent diameters from 2 to 25 µm, in solidified A356. A total of 700 micrographs, acquired with a standard white light microscope with 10 x magnification, were analyzed. The applied software (Image Pro-Plus 7.0 from MediaCybemetics®) allows for programming of macros which in tum provides the user with a higher degree of control. The automated results are compared with the results obtained by manually counting the particles in the same micrographs. The impact of the automated results on the estimated filtration efficiency was established to be only -3%.IntroductionInclusions are both indigenous and exogenous particulates that are present in commercial metals such as aluminum. If large individual or large numbers of inclusions are present, they can have a significant negative impact on the appearance, mechanical and chemical behavior of products produced from the metal. Aluminum is known to contain large numbers of inclusions: =50 µm in size, e.g. typically <l ppm by volume or <100,000 inclusions of>20 µm per kg of metal as detectable using a Liquid Metal Cleanliness Analyzer, LiMCA [1]. Depending on the final application of the aluminum, inclusions can render the metal 'not fit for purpose', and result in serious economic consequences to metal producers.It is not surprising that the aluminum industry has developed a number of treatment processes to improve metal cleanliness, given the large number of high value products whose quality can be adversely affected by inclusions. CFFs are the most commonly applied filtration process and have been used to filter >50% of the world production of aluminum since the 1990's [2].Inclusions in aluminum may be particles, bifilms [3] or clusters of: oxides (Al2O3 , SiO2), spinels (MgO· Al2O3), carbides (SiC, Al4C3), nitrides (AlN), borides (TiB2), sulfides, phosphides and intermetallics [ 4]."

Jan 1, 2013

By Xuan Cheng

The electrochemistry of sulfide mineral flotation is reviewed with particular emphasis on galvanic interaction among minerals and grinding media, and its relevance to flotation of complex sulfide ores is discussed. Surface alteration due to galvanic interactions among chalcopyrite, pyrrhotite and mild steel is analyzed in terms of voltammetric and chronoamperometric studies on individual minerals and through galvanic current measurements in 2- and 3- electrode combinations. The results are related to laboratory flotation behaviors of chalcopyrite-pyrrhotite mixtures simulating copper-nickel bearing Duluth gabbro.

Jan 1, 1993

By Moto Goto

Onahama Smelter of Onahama Smelting & Refining Co., Ltd. has two green- charge reverberatory furnaces; the old furnace was constructed in 1965 and the new one in 1973. This paper discusses the use of oxygen-oil burners in a green-charge reverberatory furnace and also compares the copper loss in slag between the two furnaces at Onahama Smelter. During the past ten years of operation, no shutdowns of the old furnace were necessary and the smelting capacity was increased by 25% by the use of two oxygen-oil burners. These burners are suitable for a green-charge reverberatory furnace to in- crease the smelting capacity without causing an increase of the exhaust gas volume and refractory erosion. After two years of operation of the old furnace, a bottom build-up in the charging zone of approximately 50 centimeters was experienced, and this build-up has stayed at this level since then. In 1973, a new additional reverberatory furnace was put into operation. Copper content in slag of the new furnace was lower by approximately 0.15% than that of the old one during the first several months after the start-up. Investigations were then made on the effect of the bottom conditions in the charging zone on the copper content in slag.

Jan 1, 1976

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