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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 R. J. Wesely

The paper describes the various methods which are currently being used or considered to refine gold and silver. These methods are then compared on a technical and economic basis. Conclusions are drawn on the factors which might influence the choice of process for different feed stocks and economic constraints

Jan 1, 1990

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 Tailoka F.

Various metallurgical residues from iron and steel making processes have been treated by chlorination in excess air with hydrogen chloride gas generated from the combustion of scrap polyvinyl chloride (PVC). The residues include dust from both the electric arc and blast &maces, hydrocyclone overflow, zinc - lead blast furnace slags and dust rich in zinc and copper from copper refining. Chlorination is achieved either directly by mixing the residues with scrap PVC or indirectly in a two furnace system. In the latter, scrap PVC is combusted between 523 and 573 K in a horizontal furnace and the resulting gases are then reacted with metallurgical residues in a vertical furnace at 1166 to 1329 K. Gas chromatography, thermogravimetric measurements, XRD and AAS have been utilised to study the reactions. The recovery of non ferrous metals is as high as 80 to 90 % and only a negligible amount of iron is carried over. The optimum temperature for combustion is between 518 and 573 K. Above 600 K, the evolution of HCI is so fast that sufficient chlorination is not achieved. Analysis showed that no dioxins were present in the gases, the residues or the chlorides.

Jan 1, 1997

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

By R. Craig McClung

Contrary to other sulfide minerals, where recovery is principally liberation controlled, the recovery of molybdenite is more complex. It is this complexity that initiated a geometallurgical investigation of molybdenites from Bingham Canyon. The aim of this investigation was to determine the effect mineralogy and/or mineralogical attributes have on recovery. All samples were analyzed using normal mineralogical techniques. The results reveal the presence of two distinctly different types of molybdenite. These have been identified as the two polytypes of molybdenite: i.e. hexagonal (2H); and rhombohedral (3R). The 2H-polytype occurs as textbook-shaped particles in quartz-molybdenite veins that are located in the current pit bottom. The 3R-polytype occurs as disseminated, “ball”-shaped particles with a dull or frosted appearance and are concentrated along the margins of the current pit. Concerning their metallurgical behavior, each type exhibits unique metallurgical properties that are consistent with those reported in the published literature. The 2H-polytype is easily ground and kinetically “faster” floating with surface attributes that are amenable to higher rates of recovery. This results in the production of a high quality concentrate under normal operating conditions. The 3R-polytype, by comparison, is difficult to grind and kinetically “slower” floating with surface attributes that are less amenable to recovery. Therefore, in deposits with higher concentrations of the 3R-polytype, modifications to the normal operating parameters may be necessary to improve recovery. This investigation highlights the necessity for understanding the mineralogical characteristics of any economic mineral(s), as these will have a direct impact on recovery.

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 Thomas E. P. Wechsler

The limiting factor for most pyro-metallurgical processes in secondary cop- per melting is the time required to heat and melt the product. American Combustion&apos;s proprietary PYRETRON variable £uel/air/oxygen combustion system improves the throughput of existing scrap melting and heating furnaces for copper and copper alloy production by increasing the rate of heat transfer from the flame to the product. The increased productivity and energy savings obtained from this technology can result in sizable reductions in operating costs for smelting operations.

Jan 1, 1991

By Liow Jong-Leng

A survey of the interactions of large gas bubbles formed from top and bottom injection of gases into melts was carried out. Spherical cap bubbles were found not to produce much splash when they break through the bath free surface except for that formed by plunging of the-spout at its edges. In contrast, the bursting of balloons produces cavities which give rise to liquid jets being ejected from the bath free surface. The position of the balloons relative to the bath free surface is an important parameter in the formation of the liquid jet. It is found that the interactions of multiple bubbles close to the free surface is important in determining the splash behaviour of gas injected systems.

Jan 1, 1996

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 Alysson Tadeu Pereira Almeida

Steels with low concentrations of nitrogen, hydrogen and carbon have been in large demand lately. The RH process is a secondary refining process that can simultaneously attain significant levels of removal of these interstitial elements from liquid steel. In the RH process, the melt circulation rate plays a very important role in determining the productivity of the equipment, since it affects the decarburization rate. In the present work, a physical model of a RH degasser in a 1:5 scale of an industrial reactor has been built and used in the study of the circulation rate and of the kinetics of decarburization. The effects of the gas flow rate and of the configurations of the nozzles used in the injection of the gas have been analyzed. The decarburization reaction of liquid steel was simulated using a reaction involving CO2 and caustic solutions. The concentration of CO2 in the solution was evaluated using pH measurements. The experimental results indicated that the kinetics of decarburization can be described by a first order equation. Based on the results, it was possible to determine the contributions of the decarburization in the upleg snorkel and in the vacuum vessel.

Jan 1, 2006

By M. W. Kennedy

Prediction of the thermal duties of copper coolers in freeze lined furnaces is challenging. Where copper coolers are immersed in liquid slag the heat transfer is often defined by a natural convection cell immediately adjacent to the wall, in the absence of other factors producing forced convection. Slag coolers are typically not fully immersed, slag temperature, liquidus and superheat can vary, and bath levels may change significantly with batch tapping, leading to substantial variations in radiation heat fluxes. Radiation heat transfer is discussed with reference to the non-obvious impact of slag liquidus on radiation losses in the exposed cooler sections. Reference is made to literature and the results of analytical and FEM models.

By Zhao Hengxian

We studied the phase diagram of Na3AlFe-ZrO system, reduction of ZrO2 by aluminium and electrochemical behaviours of ZrO2 in the system. The results show that Na3ALF6-ZrO2 system is a simle eutectic one, that the velocity of reduction of ZrO2 in the system is rapid al 960&apos;C and that the Zr content in the alloy abtained can reach as high as 2.5wt%. Potential scanning shows that there exist new current peaks on the potential scanning plats except for the cuurent peaks corresponding to the oxidation of aluminium. The method of making Al-Zr alloy in our paper has advantages over the traditional method of mixing metals.

Jan 1, 1992

By Feng Liu

A thermal upgrading process by which nickel value can be concentrated in a ferronickel alloy is a possible alternative to treat Sudbury pyrrhotite (Po) tailings with nickel content of 0.5–1.5 wt%. The basis of this process is precipitation of Ni from Po at high temperature once Fe/S ratio in the iron-deficient Po is shifted towards stoichiometric or near stoichiometric FeS (troilite) either by the addition of iron and/or the removal of sulfur. For the iron addition route, the reaction between elemental iron and nickeliferous pyrrhotite to produce ferronickel alloy and Ni-depleted iron sulfide phase plays a critical rule. In this paper, the formation mechanism of ferronickel alloy was investigated using the diffusion couple technique to better understand the nickel diffusion behavior in the iron and sulfide phases.

By Wei Luo, Yuanbo Zhang, Zhixiong You, Zijian Su, Guanghui Li, Tao Jiang

"In this study, the appropriate sintering process parameters for low-grade ferromanganese ores were investigated. The results showed that, under the condition of natural basicity (R=0.03), the optimal parameters were obtained as follows: moisture of mixture 9 .1 %, coke powder 9 .9% and sintering negative pressure 7 KPa. And the corresponding yield, ISO tumbling index and utilization coefficient reached at 80.18%, 61.27% and 1.515t·m-2·h-1, respectively. Under the optimal parameters, the emission of harmful gases, such as S02 and NOx, were reduced evidently with 30% of coke powder replaced by biomass charcoal. Moreover, it was found that the basicity had obvious effects on the quality of the sinters when it changed between 0.03 and 2.4. The ISO tumbling index gradually decreased from 61.27% to 55.47% with the basicity increasing from 0.03 to 1.2, then, it began to increase after the basicity further increased to 2.4.IntroductionManganese is mainly consumed by steel and battery industries, particularly in the steel plants and ferroalloy units. The consumption of metal manganese in the ferroalloy industry accounts for 85%-90% of the total Mn [1-2]. Therefore, ensuring sufficient manganese alloys is essential to meet the rapid development of steel industry. Recently, rich-manganese slag containing high grade Mn (>40%), low Fe (1%) and P (<0.03%) is considered as superior raw materials for manganese alloys. While the sinters made from manganese ores are major raw materials for producing rich-manganese slag with the increasing exhaustion of natural rich manganese lump ores [3-5]."

Jan 1, 2013

By Francis Vanbellen

Umicore Precious Metals Refining operates an integrated precious metals smelting and refining plant in Hoboken, Belgium. Once a smelter and refiner of complex concentrates, the plant today?s feed consists exclusively of industrial and consumer recycled products, making it the world?s largest recycling facility for precious metals. Unlike the fairy tale of the Frog Prince, it took much more than a princess? kiss to successfully realize this makeover. A completely renewed plant has been built over the past decade. The most visible technological innovation was the commissioning of the Pb-Cu smelter. Its flexibility towards very different types of feed makes it perfectly suited as main entry to the Hoboken flow sheet. A new Cu-leaching & electro winning plant and precious metals refinery make up the Precious Metals Operations (PMO) whose targets are fast throughput and maximized yields for gold, silver and the platinum group metals. The Base Metals Operations (BMO), flexibly process the by-products from the PMO, valorizing ?impurities? like indium, tellurium, selenium and others. Off gas and waste water treatments ensure compliance with strict environmental standards. Precious metals recycling is an art that goes beyond mastering a unique flow sheet. Umicore Precious Metals Refining offers a complete recycling service, taking care of sampling and assaying, metals management and logistics. The quality of this integral service is recognized through the attribution of ISO certifications for our operational activities, sampling and the environmental care. And it?s an art that follows Michelangelo?s experience: ?Art is 5% of inspiration and 95% of transpiration.?

Jan 1, 2006

By Ph. Cauwe

This paper presents the experience that NESA and MECHIM have gained about recovery of non ferrous and precious metals from complex sulfide materials. Processed materials are from natural deposits or metallurgical by-products or residues. Roasting of these materials is closely related to the pyro or hydrometallurgical processes used downstream of the roasting. Conditions of a first step of roasting the SELECTIVE ROASTING, are analyzed and explained. The roasted products so obtained are characterised by an extended elimination of volatile sulfides (AS, Bi, Sb, Sn, Pb, Hg, ?? ) and are readily available for the pyrometallurgical recovery of non ferrous and precious metals. After the SELECTIVE ROASTING, thanks to. the high porosity obtained in the "selective calcine", the SULFATE ROASTING is per-formed in excellent conditions. Hydrometallurgical tests performed for the final calcine show a high recovery of non ferrous and precious? metals and require only simple and well known processes. Many experimental and commercial data are given.

Jan 1, 1983

By M. B. Sizgoric

Quantitative mineralogy is used in a study done on an Inco Metals Company nickel sulfide occurrence from &apos;the Thompson area in Northern Manitoba. The study included: a) determination of the variations in chemical composition of the ore minerals; b) determination of the liberation of the ore minerals for the various types of ore and for different feed grinds; c) assessment of the preliminary mill test results by comparing the mineral distribution in the different tailings. Preliminary mill test results had outlined three main problem areas: 1) unacceptabiy low grade concentrate with, 2) very high weight recovery and, 3) low pyrrhotite rejection resulting in a high sulfur concentrate. The mineralogical study readily explained these results by showing that: 1) between 20 and 40% of the nickel in the feeds and 55 and 75% of the nickel lost in the tailings is associated with pyrrhotite. This accounts in part for the low grade of the concentrates obtained at high recoveries: 2) hexagonal nonmagnetic pyrrhotite constitutes over 90 percent of pyrrhotite. Since hexagonal pyrrhotite floats more readily than monoclinic pyrrhotite, this could be part of the reason for the undesirable high pyrrhotite recoveries into the concentrates. Further test work to establish both the optimal grind and the best conditions for pyrrhotite rejection is therefore mandatory.

Jan 1, 1981

By William A. Hockings

This report describes the results of laboratory studies on leaching of copper ores.tlf These studies are the first step of a program for the investigation of in situ leaching of tabular, metalliferous ore bodies.(2) The basic steps required in the development of an in situ process are: 1. Leachability - the ability to dissolve the metal values from the ore under in situ conditions must be demonstrated. 2. Ore Preparation - the ore must be prepared so that sufficient contact with the solution can be attained. 3. System Design - integrated in situ systems must be designed and studied for engineering feasibility. 4. Economic Feasibility - the economics of the system must be shown to be economically feasible and competitive. 5. Environmental Feasibility - the loss of reagents into the environment must be investigated. 6. Pilot Scale Testing - the feasibility of the system must be demonstrated on a sufficiently large scale. The studies described in this report were concerned only with the first step of the program, viz., leachability. Native and sulfide copper ores from the Michigan copper district were selected as model ores for these studies. Aqueous amnonia solutions were chosen as the solvents to be investigated. In this study carbonate (CO3, HCO3, H2CO3) was used exclusively as the anion. In keeping with custom it is referred to as carbon dioxide and concentrations are ex- pressed in terms of CO2. When leaching native copper the reaction is

Jan 1, 1976

By F. E. Pawlek

Copper concentrates can be comminuted in an attritor within a very short time to a particle size of 1 - 0.1 um. Addition of sodium hydroxide enhances commninution. The concentrates, suspended only in water, can be completely dissolved under oxygen over pressure and temperatures ranging from 120 - 180°C (248 - 356°F), because the surface area of the concentrate has been significantly increased by the ultra fine grinding. Addi¬tion of a small amount of silver ions to leach liquor containing sulfuric acid acted as a catalyst for the dissolution of chalcopyrite, because of the formation of local elements on the surface. The addition of C1- ions was also catalytically very effective. With this method it is possible to completely dissolve the copper contained in chalcopyrite concentrates after ultra fine grinding within 30 min at 110°C (230°F) under an oxygen partial pressure of 1 atm (14 psig). Several flowsheets demonstrate the industrial feasibility.

Jan 1, 1976