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By Hiroaki Kawamura, Takeshi Yoshikawa, Kazuki Morita, Yutaka Yanaba

"To develop an alternative metallurgical process for phosphorus removal in the production of solar-grade silicon (SOG-Si), slag treatment of metallurgical-grade silicon (MG-Si) was conducted, followed by acid leaching. Phosphorus-doped silicon alloy or MG-Si containing certain amounts of phosphorus and calcium was reacted at 1723 K and 1773 K with CaO--CaF2 of several compositions. Phosphorus removal from the molten silicon into the slag phase was confirmed by reduction to phosphide ions, P3-, and phosphate ions, P3-. These ions were separately determined using a wet chemical analysis method developed by ourselves. The highest phosphorus distribution ratio obtained was 2. 7 after reaction for 18 h with 17.5 mass% CaO--CaF2 slag. We then conducted acid leaching of the silicon and achieved removal of a large fraction (over 90 % ) of the phosphorus, which was much higher than that obtained by ordinary oxidizing slag treatment.IntroductionIn recent years, the production of solar cells has been increasing rapidly. Because of this, the demand for solar-grade silicon (SOG-Si) has also been growing rapidly. The development of lower-cost mass production processes is therefore needed to provide silicon feedstock. Phosphorus is one of the impurities in metallurgical-grade silicon (MG-Si). Because of its large segregation coefficient (kp = 0.35) [l ], it is difficult to remove phosphorus using a solidification refining process. Vacuum melting is considered to be a promising method for removing phosphorous from MG-Si [2], but the issues of high cost and large energy consumption have still to be resolved.Slag treatment is often used to remove impurity elements by oxidizing reactions during general oxidation refining processes. For example, phosphorus in molten steel is removed into a slag phase as phosphate ions, PO4 3-l-, by the following reaction:"

Jan 1, 2013

By Haotian Xue

A new process to extracted antimony directly from stibnite concentrate by reductive sulfur-fixation smelting in sodium molten salt has been presented. The influences of sodium salt content and composition, ferric oxide addition, temperature and time was investigated, respectively. The optimum conditions was determined as follows: W????: ??concentrate=40%, W??alt: ????concentrate =88.75%, WFe2O3 :Wconcentrate =55.13%, W??aCl: ????alt=40%, 1123K, 1h. Under above-mentioned optimum conditions, the average direct recovery ratio of antimony can reach 91.48%, and the main chemical composition of obtained crude antimony is Sb 94.31%, Fe 4.436%, Pb 0.502%, Au 0.0236%. In comparison to traditional antimony pyrometallurgical process, the smelting temperature of present process is reduced from 1423~1473K to 1123~1173K. During the smelting operation, SO2 emision can be avoided completely due to sulfur-fixation as FeS. Furthermore , S0 can be obtained when the molten slag is handled by water leaching with conditions of 323K, L/S=5/1, 2h.

Jan 1, 2014

By Baptiste Laubie

Agromining is a phytotechnology aiming at producing commercial metal compounds from low-grade ores thanks to hyperaccumulating plants. The fern Dichranopteris dichotoma is a rare earth element (REE) hyperaccumulator, which naturally grows on former mine tailings in China. It accumulates up to 0.35% of REEs in its aerial parts. Different hydrometallurgical processes are currently developed to recover these elements directly from the biomass or from ashes after combustion. The process presented here consists of a direct extraction by EDTA solution, followed by precipitation with acid oxalic. Optimal precipitation pH and influence of organic matter are determined by modelling and by experimental studies. The final solid contains 4.3% of REEs, with calcium as the main cationic impurity (0.45% of the precipitate). The recovery yield is similar for major REEs and is around 70%. After optimization, upscaling of the process will allow the agromining development to recover REEs from secondary resources with more environmentally friendly techniques.

By Rolando Campos

In August 1993, the operation of Refimet Chile's copper custom smelter commenced at La Negra, near Antofagasta in northern Chile. Design smelter throughput corresponded to 235 000 tonnes of concentrate, calcines and copper cements arising from suppliers in the north of the country to produce 90 000 t/y of blister copper. Refimet had initially gained experienced in building and operating leaching, roasting and a blast furnace facility at Rungue, near Santiago, followed by Roasting at La Negra. The initial smelter project was based on conventional reverb- smelting and Peirce-Smith converting and the majority of equipment was 'purchased second-hand and rehabilitated or modified. After only 3 years in production, the treatment capacity was significantly improved by introduction of technical improvements to the original plant operating scheme. Recently, the plant was further expanded to an annual smelting capacity in excess of 400 000 t/y feed, corresponding to around 160 000 t/y copper production. This expansion, referred to as Phase 2, was achieved by modification of the reverb to oxy-fuel firing, addition of a further (second-hand) acid plant, fire refining and anode casting facilities. Parallel development of concentrate injection into enlarged converters-also took place. Following successful commissioning of Phase 2 expansion, initial engineering studies for a third expansion phase have been completed. This aims to use leading technology based on bath smelting of bone-dry concentrates in a Continuous Reactor. This paper provides an overview of the relatively short plant history, its development and improvements together with operating indices achieved.

Jan 1, 1998

By Renxing Li, Yongyong Gong, Yufeng Cheng, Zhenxing Yin, Xin Cao, Qijie Zhai

"This paper investigated the refinement effect of pulse magneto-oscillation (PMO) on the solidification structures of medium carbon steel S45C in metal mould. The induction coil was positioned at the middle of ingot. The results showed that solidification structure of the treated ingots was remarkably modified with a transformation from well-developed dendritic structures to small dendritic structures or globular structures compared to the untreated ingot. The area fraction of modified microstructure regions reached more than 80 percent. A further experimental investigation had been done to understand the influence of refinement effect on the solidification structure under different mould size. Theoretical analysis demonstrated that the mechanism for the refinement of solidification structure was that PMO promoted nucleation near the mould walls and changed the interface temperature gradient and concentration gradient in liquid, eventually leading to a transition from the columnar crystals to the equiaxed crystals.IntroductionIn recent two decades, the electromagnetic processing of materials (EPM) has been widely used in many fields such as ironmaking, steelmaking, and solidification processing [1-6], where EPM can control melt flow, modify melt shape, reduce macro-segregation and refine microstructure. Pulse magneto-oscillation [7-9] (PMO), as a novel technique of EPM, has a remarkable effect on grain refinement and high potentiality to be used in industrial production. Compared with ultrasound refinement technique, PMO can be easily employed to metal solidification processing for long time in no contact with hot metal liquid by using a water-cooled coil. Another important advantage is that PMO needs smaller energy compared to pulsed magnetic field which needs a very high current to obtain a strong magnetic field to get a satisfactory effect. These advantages mentioned above are beneficial for industrial application, which make it potential to be widely used in future. Gong et al. [7] have studied the refinement effect of PMO on pure aluminum and find that PMO can significantly modify the solidification structure of pure aluminum. Li et al. [9] have reported the effect of temperature field on solidification structure under the influence of PMO. On the basis of these works, this paper has studied the effect of PMO on solidification process of medium carbon steel S45C in a metal mould, which can also provide some information for industrial application of this new technique."

Jan 1, 2012

By Viktor Ashikhin, Pavel Arkhipov, Yurii Zaikov

"Lead alloys electro-winning from chloride melts was under investigation. Impurities concentration in cathode lead is strongly depended on temperature, electrolyte composition, anode current density. The equilibrium electrode potentials of lead-antimony alloys with the various content of electropositive metal in the alloy were investigated in the wide temperature interval. Thermodynamic properties of Pb-Sb alloys containing 20-95 mol% of Pb were studied by EMF method in temperature interval 723-873K in molten mixture of potassium and lead chlorides. Partial and integral thermodynamic characteristics were calculated. Small negative deviations from Raul’s law were found. Anode processes were investigated. The lead dissolution was found to be the only process in certain interval of current densities and electropositive metal content in alloy.IntroductionAt present human race is facing the problem of pollution by lead and its compounds and also the pollution influence on population health all over the world. One of the solution ways is the recycling lead containing technical wastes by ecologically clean technologies.World scientific community pays much attention to the electrolysis of molten salts. The usage of salt mixtures, as electrolytes, discovers new possibilities in the production of metals, metal compounds and alloys. ?????????? of the electrolysis at the temperature 50 - 200 °? above the melting temperature of chosen salt mixture allow to unbreaks processes, that undergo in the pre-electrode layer. The rate of the electrodepositing of elements are much higher than in the water electrolytes. At present there are technologies developed for production of metals (Ta, Nb, Ti, Zr, Hf, Ca, Al, Mg, Be, Li and others) by the electrolysis of the melts. Electrolysis of melts might be used in order to convert different technological formations containing lead and other nonferrous metals, that produced by different enterprises. According to the level of the influence on the living organisms lead is in the group of highly dangerous substances alongside with arsenic, cadmium, mercury, selenium, zinc, etc. Toxity and ability to accumulate in the human organism are two main sources of danger for the human being."

Jan 1, 2008

By M. Nienoord, O. S. L. Bruinsma, J. A. F. M. Schade Van Westrum, W. H. Sillekens, B. Mehmetaj

Recycling of aluminium is an effective way of enhancing the efficient use of energy and limiting the burden on the environment. Where cascade recycling is an established way of using reclaimed aluminium, closing the recycling chain is currently hampered by the unavailability of suitable techniques for refining contaminated scrap on an industrial scale. To overcome this problem, purification based on fractional crystallisation appears to be a promising option. This implies that the material is to be processed in the semi-solid state; that is, at a temperature where a solid and a liquid phase co-exist. In the current paper, it is shown that zone melting can serve as an indi.cative test for assessing the refining potential of fractional crystallisation processes, since they are both based on the same thermodynamic principle. Next, the results of zone-melting experiments are presented for some representative aluminium model alloys. The BPS-model (developed by Burton, Prim and Stichter) is used to interpret these results, from which it is concluded that the model needs extension to obtain a predictive tool for fractional crystallisation processes.

Jan 1, 2000

By Ali Unal, Ali I. Kahveci

Alcoa developed a fractional crystallization process some 30 years ago as a method to purify aluminum. Depending on the purity of feed metal, it has been commercially used to make 3N7-6N purity aluminum. As an extension of this technology, Alcoa has experimented with purifying various aluminum alloy scrap for the purpose of recycling. Purified aluminum alloy scrap can be reused for making the same alloy. This presentation will discuss Alcoa fractional crystallization technology and its application to alloy scrap processing. Process capabilities and the partitioning of eutectic and peritectic impurities during fractional crystallization will be discussed for the alloy systems investigated.

Jan 1, 2000

By Alexandr I. Volkhin

It is practically useful to separate copper from nickel at the fire refining stage of blister copper by transferring nickel in electrochemical inert silicides which are being concentrated further into the tank-house slimes. The treatment of copper melt by silicon-containing reagents is resulted in lowering the interfacial tension of the melt, its deoxidizing, selective siliconizing of in-melt nickel and forming a by-product with fluxing properties. Si-containing reagents have positive influence on results of fire and electrolytic refining, and further pulverizing of copper in plant conditions.

Jan 1, 2006

By Musa Karakus

Reflected light microscopic (RLM) examination of dust particles from lead and copper smelters can effectively characterize their mineralogy, texture, and origin. Scanning electron microscopic-energy dispersive spectroscopic (SEM-EDS) analysis provides confirmation of the optical identifications and chemical data on the phases. Studied lead smelter dust samples were from the: I) blast furnace, 2) sinter plant scrubber, 3) sinter plant crusher, 4) dross furnace, and 5) refinery. Phases identified included galena fragments, melted PbS, metallic Pb and Cu, Cu-Ni, Cu-Zn, Zn-Ag, Zn-Cu-Ag, Ni-Cu-Sb, and Ni-Cu-Zn-Ag metal alloys, Ni-sulfide, Cu-sulfide, and Cu-Pb-sulfide dross .phases; slag and sinter particles, coke fragments, unreacted original feed phases: pyrite, chalcopyrite, sphalerite, siegenite, bravoite; and oxidized particles: iss, bornite, chalcocite, covellite, magnetite, hematite, and goethite. Dust from a secondary copper refinery were found by RLM and SEM to consist of tenorite, cuprite, cassiterite, two silicate phases. Magnetite, hematite, Fe-Al-Cr-Mg spinel, periclase, forsterite, and wollastonite were derived from the furnace linings during initial cleaning.

Jan 1, 1992

By Ann M. Hagni

Reflected Light Microscopy (RLM) And Scanning Electron Microscopic-Energy Dispersive Spectroscopic Analysis (SEM-EDS) Study Of Electric Arc Furnace (EAF) Dusts Have Shown That Their Mineralogy Is Complex And Varied. The Particles Are Largely Spherical, And Can Be Seen In RLM Sections To Be Composed Of Franklinite, And Zincite, But They Show Significant Solid Solution With Each Other And May Contain Small Amounts Of Chromium. These Crystalline Phases Occur As Crystals And Skeletal Growths Within Ca-Fe-Si Glass. Because Chlorine Is A Deleterious Constituent In Recovered Zinc Products From EAF Dusts, Special Attention Has Been Given To Chlorine-Bearing Phases, And They Include Hydrophylite (Cacl2), Lime (Cao), And Organic Phases. Pyrohydrolysis-Treated EAF Dusts With Silica (Si02), Tungstite (W03), Alumina (A1203), And Bunsenite (Nio) Additives Contain Franklinite, Scheelite (Cawo4), Willemite (Zn2SiO4), And Hematite (Fe2O3)

Jan 1, 1992

By John A. Mavrogenes

Reflected light microscopy and electron microprobe techniques were used to determine the mineralogy, phase percentages, grain sizes, and textures of Co-Ni-rich mattes. The mattes were produced by submerged bath smelting at the University of Missouri-Rolla Pyrometallurgical Center of a flotation concentrate with 4.S% Co and 5.1% Ni that was prepared at the United States Bureau of Mines Rolla Research Center by flotation up-grading of the cobalt and nickel content of a copper concentrate from the Magmont mine, Viburnum Trend, Southeast Missouri. Nine distinct phases were distinguished in the matte samples, and three of these contain cobalt and nickel. The phases that were free from cobalt and nickel are bornite, chalcocite, pyrrhotite, magnetite, metallic copper, and galena. Submerged bath smelting serves to segregate the cobalt and nickel into phases that can subsequently be recovered by flotation. These phases are: shandite (Ni3PbZSZ)' cobaltpentlandite ((Co,Ni,Fe)9SS)' and Co-bearing Fe-rich sphalerite ((Zn,Fe,Co)S). Most of the cobalt occurs in cobaltpentlandite, but some is present in sphalerite. High total air conditions during smelting favor the development and segregation of cobalt into cobaltpentlandite. Nickel occurs in cobaltpentlandite and shandite. Shandite contains lead, a deleterious constituent in the smelting of cobalt and nickel.

Jan 1, 1989

By Richard D. Hagni

Polished sections of pyrometallurgical intermediate products from a simulated commercial flash furnace were examined by reflected light microscopy, scanning electron microscopy-energy dispersive spectrometry and electron backscatter analysis, and microprobe analysis for phase and textural relationships. The smelter feed is a copper concentrate from a porphyry copper deposit. The concentrate consists primarily of chalcopyrite, bornite and pyrite with smaller amounts of covellite, chalcocite, molybdenite, magnetite, galena, and sphalerite. The flash furnace reactions for pyrite and chalcopyrite can be observed by reflected light microscopy. Reacted angular particles of pyrite exhibit successive rims of fibrous pyrrhotite and hematite or magnetite. Reacted angular chalcopyrite particles show successive rims of bornite, digenite, and chalcocite. Spherical particles, formed by the complete melting of former pyrite particles, consist of variable amounts of granular pyrrhotite with magnetite rims and minor hematite. Spherical particles, formed by the complete melting of former chalcopyrite particles, exhibit exsolution intergrowths with varying proportions of intermediate solid solution, bornite, digenite, and chalcocite and have rims of hematite, magnetite, and copper-iron spinel. Sphalerite and molybdenite do not show evident mineralogical reactions.

Jan 1, 1987

By Christopher B. Vierrether

Reflected light microscopy, scanning electron microscopy, and electron microprobe analysis have been used to determine the mineralogy, phase percentages, grain sizes, textures, and partitioning of cobalt and nickel in two cobalt-nickel rich mattes. These mattes were prepared by submerged bath smelting from a flotation cobalt-nickel concentrate containing 4.8% cobalt and 5.1% nickel. The concentrate was derived from lead-zinc-copper ores of the Viburnum Trend, southeast Missouri. Eleven discrete phases have been distinguished in the matte samples, three of which contain significant cobalt and nickel. The phases are cobaltpentlandite ((Co,Ni,Fe)9S8), cobalt-bearing marmatite ((Co,Fe,Zn)S), shandite (Ni3Pb2S2), bornite (Cu5FeS4), galena (PbS), magnetite (Fe3O4), pyrrhotite ((Co,Ni,Cu,Fe)1_xS), chalcocite (Cu2S), CuPbS phase, metallic copper, and metallic silver. Cobaltpentlandite and cobalt-bearing marmatite- occur in coarse grains (50 µm) that would separate readily during grinding, but shandite contains small (5 - 10um), abundant inclusions of pyrrhotite and bornite.. Some mineralogical variations between the two matte samples were due to differing degrees of oxidation during smelting,

Jan 1, 1988

By XING Xiangdong, Zhang Jianliang, MA Jinfang, WANG Zhenyang

The non-equilibrium reflux reaction behavior of phosphorus was studied with synthetic slags formed by using the AR chemical reagents and changing the initial condition of basicity, FeO, MgO and Al2O3. Due to increase of viscosity, the dephosphorization slag with high basicity inhibits the full contact of slag with iron, which leads to the low reaction rate in the early stage. However, since the high basicity improves the activity coefficient of CaO, the dephosphorization rate and phosphorus capacity goes up in late reaction stage. FeO promotes the increase of reaction rate in early dephosphorization stage. But the polarization force of Fe2+ is stronger than Ca2+, which hinders the reaction between phosphate ion and CaO and reduces the stability of PO4 3-. Thus, high content of FeO will adversely impact on dephosphorization reaction. In addition, MgO has a promoting effect to the dephosphorization, whereas Al2O3 has a negative influence.

Jan 1, 2016

By Carlos Maurício Fontes Vieira, Sergio Neves Monteiro

"A ceramic body traditionally used to produce bricks and roofing tiles with kaolinitic clays was reformulated by the addition of sand and illitic clay. The objective was to obtain a ceramic product with better technological properties. Specimens were made by uniaxial press-molding at 20 MPa and then fired at 850, 900 and 950°C. The determined technological properties were: linear shrinkage, water absorption and flexural rupture strength. The results showed that both sand and illitic clay contribute to reduce the water absorption of the industrial clayey body. With respect to the flexural behavior, it was observed that the incorporation of sand decreased the mechanical strength. On the other hand, the illitic, incorporated in an amounts of 30 wt.% contributed to increase the mechanical strength of the clayey ceramic.IntroductionCeramic bodies industrially fabricated in the county of Campos, north of the State of Rio de Janeiro, in Brazil, are still empirically elaborated using a mixture of local clays. These clays are predominantly kaolinitic mineral in nature, associated with high plasticity and elevated weight loss during the firing stage. Due to the excessive plasticity of the ceramic bodies, dimensional defects, which occur after drying and firing are usually obtained. Moreover, the kaolinitic nature and the presence of aluminum hydroxide (gibbsite) confer a refractory behavior to the local clays, which impairs sintering during the firing operation. In the case of clay ceramic products for civil construction, this results in greater porosity associated with elevated values of water absorption and low mechanical strength [1,2]. To avoid these problems, it is necessary to reformulate the ceramic body composition. The addition of both non-plastic materials to reduce plasticity and fluxes to condition the refractoriness is a possible alternative.As an alternative to reduce the plasticity of clayey ceramics sand, which is predominantly constituted of silica, can be used. The incorporation of sand in amounts of up to 25 wt.% to a clayey ceramic body used for roofing tiles fabrication was studied by Vieira et al. [3]. In that work specimens were prepared by extrusion and fired at 850°C. The results indicated that in the pre-firing stages the sand improved the workability of the investigated clayey ceramic body and facilitates the drying stage. It was also observed that the incorporated sand significantly improved the physical and mechanical properties of the clayey ceramic after firing. On the other hand, the apport of flux oxides could be done by the use of illitic clays that have a higher amount of alkaline oxides in comparison with the kaolinitics clays."

Jan 1, 2013

By L. J. Davies

Refractories usage in furnaces for the extraction of nickel from both sulphides and lateritic ores is reviewed. Recent changes in raw materials and basic brick qualities developed to meet the increasing demands of existing and new processes are outlined. Examples of used brick examinations to establish mechanisms of wear are given. The importance of physical and chemical properties are discussed. The use of simulative laboratory testing to aid in refractories development and selection is described.

Jan 1, 1988

By V. Reiter, K. Reinharter, C. Wenzl, D. Gregurek, A. Spanring

The refractory linings in lead furnaces are exposed to several stresses rather complex in their interaction. In the present study the magnesia-chromite brick out of a lead recycling furnace suffered from a high chemical attack by the process slag. The high CaO, BaO and sulfur bearing silicate slag, as well as a high NaO2 supply from soda resulted both in a deep-reaching infiltration of the brick microstructure and a severe corrosion of the brick components. Both the sintered magnesia and chromite were attacked chemically. The FactSage calculations showed the formation of high amounts of liquid phase in the infiltrated microstructure. Further phenomena affecting the refractory performance such as iron oxide attack, redox effects, and boron attack are also discussed in the paper. The obtained information and insights serve as a basis for improving refractory materials (i.e., choice of refractories for individual process and new developments) and consequently furnace operations.

Mar 1, 2017

By K. Yarnaguchi

In the Mitsubishi Continuous Copper Converting Furnace, calcium femte slag is used. Due to its extremely high basicity, the improvement of corrosion resistance of the refractory lining is in need. In order to clarify the corrosion mechanism and to search for a new corrosion resistant material, first, the surface snuctures of bricks corroded in molten slags were observed by EPMA. Second, the dissolution behaviors of sintered MgO-based pellets containing various oxide additives were examined. It was found that the formation and the dissolution of magnesiofemte at the surface of the bricks play an important role in their corrosion and an addition of NiO, Mn02, or Ti02 to MgO is effective in stabilizing the magnesio-femte and improving the corrosion resistance of MgO.

Jan 1, 1994

By D. R. Kreuzer

The sulfide smelting industry is striving for up-scaling their operations by increasing the throughput and efficiencies of the furnaces. The physical phenomena related to refractory materials prevailing in smelters and furnaces are highly complex. The refractory materials are exposed to fairly high temperatures, thermo-mechanical stresses, penetration of pores, erosion and chemical corrosion. The application of numerical simulation tools is needed for the refractory engineering task to consider those phenomena and to evaluate the impact of operational regimes on the refractory design and finally on the integrity of the furnaces. The work discusses case studies of simulations addressing problems and questions related to the refractory design process. Practical simulation approaches which employ simplified models are introduced as the engineering process demands results in a reasonable time.