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By Yoichi Takeda

Copper solubility in Si02-CaO-FeOx slag equilibrated with copper matte in 10% S02 atmosphere at 1573K was estimated. Essential parameters are activity coefficients of copper oxide and sulfide, oxygen and sulfur potentials and activity of copper in the slag-matte system. A large number of experiments provide proper parameters to calculate copper solubility in slag. A classical thermodynamic model postulating CUOO.5 and CuSo.; molecules assists in estimating copper solubility in slag. Additions of Si02 and CaO reduce copper solubility almost in any condition. Copper loss, that is function copper solubility and slag volume, in the silica saturated Si02-FeOx binary slag is minimally equilibrated with less than 66% copper matte while copper loss in the 50% FeOx-SiOrCaO ternary slag saturated with 2CaOSi02 is minimally equilibrated with over 66% copper matte. This slag composition has potential for continuous copper converting, direct copper production or high-grade matte production.

Jan 1, 2003

By Scott R. Giese, Lucas Dix

"Recently, there is a growing trend in the aluminum foundry industry to develop· improved melting and casting processes to produce lightweight, high-strength, and thin-wall castings for the aerospace and transportation industry. One casting method that has demonstrated industrial potential for producing clean, thinwall castings is vacuum-assisted, counter gravity casting. This process has the benefit of expeditiously and quiescently filling the casting cavity with a dramatic reduction of furnace related and reoxidation inclusions. Additionally, lower casting temperatures can be utilized because the application of vacuum during filling overcomes the resistive internal cavity pressure resulting in a finer, as-cast microstructure. The paper explores and discusses the processing and design conditions in improving the mechanical properties of A206 casting alloy using the vacuum assisted, counter gravity casting process.IntroductionThe process of metal casting has been, over the centuries, the chief production technique for components used in everyday life. However, the casting process has certain inherent problems that can adversely effect the properties of a finished product. These problems are directly attributable to the gravity pouring technique used to transfer molten metal to the mold and to fill the mold cavity.A recent study for the American Metalcasting Consortium demonstrated reoxidation products created during the casting process are five times more likely to cause product rejects than entrapped molding aggregates, melt slag, or furnace lining materials1. Formation of nonmetallic and intennetallic compounds are more prevalent in aluminum and titanium alloys because of their reactiveness to furnace lining materials and their high affinity for oxygen. The incorporation of undesirable compounds can be attributed to four areas of the casting operation. The sources are charge materials, melting technique, pouring methodology, and casting cavity filling. Aluminum foundry men have addressed the first three areas by selecting high quality melt stock, non-stirring melting equipment, and the use of porous ceramic filters. Unfortunately, little consideration is given to the last, but yet tl.1e most important part of the casting operation, the actual fill mg of the casting cavity.The generation of inclusion defects during the casting process can be described by two methods. As the liquid metal flows in the gating network and casting cavity, abrupt changes in flow d1rect10n cause the metal to become agitated. This mechanism liquid metal splashing, is generated by instability of the advancing liquid metal interface from turbulence effects as schematically illustrated in figure 1a2 . The surface oxide film bursts under high velocity conditions, folds over, and becomes dispersed and incorporated in the bulk liquid. Additionally, fragmented liquid droplets ejected from the disturbed interface oxidize and become dispersed in the metal stream."

Jan 1, 2000

By Jhon Cuya

Titanium dioxide is the well-known catalyst for the photodecomposition of water in UV region and its nanoparticles show better performance than its bulk materials. Furthermore, partially sulfurized TiO2 is expected to be chemically stable and have an enhanced photocatalytic activity compared with TiO2. For this purpose, the sulfurization behavior ofTiO2 nanopartic1es was thermogravimetrically (TG) studied by a thermo-balance with a quartz spring using CS2. From the TG curve of TiO2 nanopartic1es, first, the weight decrease appeared down to around 8 wt% and then sulfurization reaction started at around 500°C at a heating rate of 1 C°/min. The weight increase curve showed a maximum of ca 30 wt% at around 750°?C and then gradually decreased to ca 12 wt% at 1000°C. This would be caused by the formation of TiS2 followed by the decomposition ofTiS2 to lower sulfides, such as Tit.0.8S2 and Ti3S4. From the comparison of the sulfurization of TiO2 nanoparticles with that of anatase, rutile and Ti(OH)4, it was found that TiO2 nanoparticles showed a similar behavior to that of Ti(OH)4.

Jan 1, 2003

By Jhon Cuya

Titanium dioxide is the well-known catalyst for the photodecomposition of water in UV region and its nanoparticles show better performance than its bulk materials. Furthermore, partially sulfurized TiO2 is expected to be chemically stable and have an enhanced photocatalytic activity compared with TiO2. For this purpose, the sulfurization behavior of TiO2 nanoparticles was thermogravimetically (TG) studied by a thermo-balance with a quartz spring using CS2. From the TG curve of TiO2 nanoparticles, first, the weight decrease appeared down to around 8 wt% and then sulfurization reaction started at around 500 °C at heating rate of 1O 'Cumin. The weight increase curve showed a maximum of ca 30 wt% at around 750 T and then gradually decreased to ca 12w% at 1000OC. This would be caused by the formation of TiS2 followed by the decomposition of TiS2 to lower sulfides, such as Til.08S2 and Ti3S4. From the comparison of the sulfurization of TiO2 nanpparticles with that of anatase, rutile and Ti(OH)4, it was found that TiO2 nanoparticles showed a similar behavior to that of Ti(OH)4.

Jan 1, 2003

By Charles H. Rawlins

Reported is work done on processing of steel mill effluents in the areas of dewatering and separation. Much of the waste from these operations is in the form of sludges from scrubbers, in which the primary constituent is iron oxide. Recycling of the sludge&apos;s magnetic fraction has become economically attractive in order to reduce the overall volume placed in landfills. The objective of this research is to determine the effectiveness of combining magnetic and cyclonic forces, to recover iron oxide particles from waste water stream, while decreasing the volume to be disposed. Three different size hydrocyclones, operating within the field of a quadripole magnet, were tested using varying feed pulp densities of magnetite, magnetite/dolomite, blast furnace (BF), and basic oxygen furnace (BOF) slurries. In the first three cases, the percentage of magnetics recovered increased to greater than 95%. The limiting operational factors are; high pulp density for small cyclones, which can cause flow blockage within the magnet field, and extremely fine particle sizes (<2 microns), which cannot be recovered. The results indicate this technique can remove virtually all the magnetic particles from some steel effluents to a 40-50% weight percent solids pulp, on an in line continuous basis.

Jan 1, 1994

By G Hope, C Young, R. N. Gow

"The presence of enargite (Cu3AsS4) is problematic in gold processing as it is refractory, increasing cyanide and oxygen consumption, and enviromnentally hazardous. Selective leaching and treatment of the arsenic would prove advantageous to conventional gold leaching methods. The reactivity of enargite samples from Montana, US and Quiruvilca, Peru were studied under alkaline conditions, pH range of 8-13, using a cyclic voltammetry corrosion cell setup. Raman spectra of the surface were taken during and after cycling to compare surface species against theoretical predominance diagrams. Under slightly oxidizing conditions, covellite (CuS) peaks were found on the surface in a short matter of time, above - 200m V vs SHE for pH 9-13, suggesting arsenic leaching, but for longer conditioning times, elemental sulfur peaks were also found, which created a passivating surface layer. By operating above pH 12, under reducing conditions, ~-500mV vs SHE, arsenic can be leached as a thioarsenate (AsS4-xOx3-), without sulfur formation.IntroductionEnviromnental limitations on pyrometallurgical processing of arsenic has pushed the desire to process enargite-, Cu3AsS4, bearing concentrates towards a hydrometallurgical solution. Attempts to process can be broken down into two categories - the co-dissolution of arsenic and copper under acidic conditions or the selective leaching of arsenic under basic conditions. The selective leaching of arsenic would preferably leave behind a chalcocite, Cu2S, or covellite, CuS, phase that would be more amenable to conventional processing methods of the copper and gold industries. These methods employ bi- or poly-sulfides to leach arsenic as Assl· [1-4], hypochlorite leaching [5-7], ammoniacal leaching [8] or fine grinding to mechanically activate the enargite surface and increase normally slow reaction kinetics[9]. This study looked into the surface formations of an enargite electrode under alkaline conditions, in a pH range from 8-13, as it cycled from -1000 mV to 1000 mV vs SHE. The understanding of the formations and under what conditions they form will be helpful in further development of any of the aforementioned processes."

Jan 1, 2012

By Tang Chaobo

According to the principles of simultaneous chemical equilibrium and electronic charge neutrality, the system of Mg(II)-NH3-CO32--SO42--H2O at 25°C has been thermodynamically analyzed. And the rule of solubility of MgCO3(s) in the system is discovered, the high dissolution field of MgCO3(s) is discovered too. Furthermore, the solubility of MgCO3(s) is increased with the increase of the concentration of SO42-, but it is decreased first then increased with the increase of the concentration of all the CO32- and the total concentration of ammonia and ammonium, and decreased with the value of pH being higher. Those results will has important significance on prepare magnesium chemical products and other salts carbonate that are strict with the content of magnesium with carburization method.

Jan 1, 2006

By Z. Smieszek, W. D?browicz, J. Pawlowski, G. Krawiec, J. Czernecki, J. Por?mbski, S. Gizicki

Rapid development of the automotive industry and motorization has been observed in Poland over the last decade. This phenomenon has increased the amount of used car batteries requiring recycling and has thus posed new challenges for their processing. Orzel Bialy" S.A, is the major secondary lead smelter in Poland. Ibis paper describes the program for smelting technology modernisation and productivity increase through the application of oxy-fuel burners, which has been implemented at "Orzel Bialy'' S.A. The main objective of smelter modernisation, which was to increase the furnace productivity by 20%, has been achieved. This paper outlines the previous and present state of the lead acid battery scrap smelting technology at the "Orzel Bialy" S.A. Specifications of the burners and of oxygen installation are given. Industrial tests with the modernised smelting technology and optimisation of the process parameters are described, and the results obtained are discussed.

Jan 1, 2000

By Stanko Nikolic

Ferrous calcium silicate slags are potentially important for future practice in copper converting operations and processes and can be described by the ?Cu2O?-FeO-Fe2O3-CaO-SiO2 system. Despite its industrial importance the phase equilibria in this system have not been fully investigated. Characterization of this slag system is necessary to improve the design and optimization parameters of new processes, including fluxing and operating temperatures. Experimental methods have been developed to investigate the phase equilibria of these slags at copper saturation and without copper. This technique involved equilibration of samples at a fixed oxygen partial pressure, rapid quenching, and analysis of the compositions of phases using electron probe x-ray microanalysis (EPMA). Liquidus and solidus data are reported for the primary phase fields of spinel, wollastonite and tridymite at 1250oC and an oxygen partial pressure of 10-6atm. The resulting data has been used to construct liquidus isotherms in the ?FeO?-CaO-SiO2 system both in equilibrium with and without molten copper. The experimental results were compared with the predictions of a thermodynamic computer package utilizing a self consistent thermodynamic database. The predictions of the model were in good agreement with the experimental isotherms when projected onto the FeO-CaO-SiO2 section, however the copper concentrations in the liquid phase at copper saturation were lower than predicted using the current database of the model.

Jan 1, 2006

By J. A. Gonzalez-Dominguez

During the electrorefining of lead by the Betts process, ionic concentration gradients become established within the slimes layer. These gradients contribute to precipitation of secondary products and to gradients in electrode potential applied to slimes filaments, and thereby affect the dissolution of noble impurities. This paper describes the experimental results obtained when a typical lead anode was dissolved under galvanostatic conditions with concurrent interruption of current at preset slimes thicknesses. Reference electrodes were incorporated within the lead anode to follow the potential gradients across the slimes electrolyte. Samples of the slimes electrolyte were withdrawn in-situ and their compositional changes were related to transport processes across the slimes layer. Upon current interruption the anodic overpotential decays, first abruptly (as the uncompensated ohmic drop disappears), and then slowly (due to the presence of a back E.M.F. created by ionic concentration gradients that decay slowly). Current interruption measurements showed that: (A) concentration gradients exist across the slimes layer, (B) inner solution potentials within the slimes layer can be larger than those measured from reference electrodes located in the bulk electrolyte, (C) secondary products can shift the inner solution potential to negative values that reverse upon re-dissolution and (D) ionic diffusion is seen upon current interruption but it is complex and difficult to model due to the presence of processes that can support the passage of internal currents. SEM and X-ray diffraction analysis of the slimes filaments indicated that secondary reactions leading to the formation of Si02 and PbF2 take place (mainly at the anodelslimes interface). The onset of these reactions and their relationship to the Pb-F-Si-H20 Eh-pH diagram are linked to the industrial operation of the Betts process.

Jan 1, 1994

By Roger Wilmoth

Exposed, open pit mine highwalls contribute significantly to the production of acid mine drainage (AMD) thus causing environmental concerns upon closure of an operating mine. Four innovative technologies were evaluated under the U.S. Environmental Protection Agency?s, Mine Waste Technology (MWTP), Prevention of AMD Generation from Open-Pit Highwalls Demonstration Project. This project is funded by the U.S. Environmental Protection Agency (EPA) and jointly administered by the EPA and the U.S. Department of Energy (DOE) through an Interagency Agreement. The objective of the field demonstration was to evaluate the technologies ability to decrease or eliminate acid generation from treated areas of the highwall in comparison an untreated highwall area. The field demonstration was performed at the Golden Sunlight Mine (GSM) a subsidiary of Placer Dome U.S., located near Whitehall, Montana. GSM is an operating gold mine. The highwall at GSM was divided into five plots measuring 15.24 by 15.24 metres (m) and each technology was assigned a plot with the fifth plot being used for comparison as a background control plot. The four technologies were spray-applied. The applied insitu treatment technologies included: 1) A modified, furfuryl alcohol resin sealant, utilizing wood and agricultural by-products to coat the rock surface. 2) EcobondTMARD, a phosphate based process that forms a stable, insoluble compound, coating the rock surface. 3) Two ARD passivation technologies, magnesium oxide and the Dupont technology developed to create an inert layer/coating on the pyrite, preventing oxidation. The technologies were evaluated using the following methods: 1) ASTM D 5744-96, Accelerated Weathering of Solid Materials using a Modified Humidity Cells, 2) mine wall residual wall rinse sampling, 3) microscopy, and 4) core drilling followed by water injection testing.

Jan 1, 2003

By cheng Peng-fei, TANG Hai-yan, guo Xiao-chen, LI Jing-she, Liang Yong-cang, Zhao Baojun

The origin and evolution of non-metallic inclusions for Al-killed casing steel during EAF-LFVD- CC process were studied by industrial tracer experiments. The formations of Al2O3 and MgO·Al2O3 micro- and macro-inclusions from ladle slag were analyzed by theoretical calculations. The results show that micro-inclusions were formed during deoxidation and temperature decreasing in the process of casting, most of the macro-inclusions come from entrapped ladle and mold slags. In addition, most of the Al2O3 formed were modified into 12CaO·7Al2O3 and 3CaO·Al2O3 inclusions which are liquid at steelmaking temperature. MnS cannot be fully modified to CaS and it was only wrapped outside the alumina or calcium aluminate in the form of (Ca,Mn)S with the amount of Ca-Si wire fed during the test.

Jan 1, 2016

By John Nauman

Liquid ferrous silicates that are related to cop- per slags have been studied as media for the transfer of heat in pyrometallurgical processes. The effective thermal diffusivities have been measured from 1025Oto 1400°C, and values in the range of 0.004 to 0.007 cm2/ sec have been obtained. The heat-transfer characteristics of these slags have been determined by measuring the rise of temperature of a cold nickel sphere immersed in the liquid slag. The sphere is spun about its vertical axis to obtain a well characterized flow of liquid about the sphere. The principal barrier to the transfer of heat from the bulk slag to the metal sphere is a solid shell of slag that forms around the sphere and subsequently melts. It appears that the detailed nature of this shell is important to theheat- transfer process. A mathematical model is used to predict the rate of heating of the sphere, and to evaluate various aspects of the system that can influence the transfer of heat.

Jan 1, 1976

By Ju Shao-hua

Although nowadays gold extraction methods are very abundant, none of them is satisfying, especially, in the field of heap leaching of low grade gold ore. The traditional heap leaching method of cyanide method plays an inglorious role of badly environmental pollution. In this paper, a bran-new and innoxious method of gold extraction system, metal-ammonium-chloride-ammonia (MACA), was proposed, and also analyzed both thermodynamically and practically. Thermodynamically, according to the principles of simultaneous chemical equilibrium and electronic charge neutrality, the thermodynamics of Au-NH4Cl-NH3-H2O system was studied by using the exponential computation method and through MATLAB programming, and the solid figure of its potential - c(NH4Cl) - c(NH4OH) was drawn. The results showed when the concentrate of ammonia is higher than 0.6 mol?L-1, fAu+/Au is only about -0.2 v. Practically, the leaching results of a cuprous gold ore showed that the extraction of gold can reach to 80% in this system. The preliminary results of reduction of the rich solution with copper and zinc powders showed that with deoxygenizing, the reduction effects were relatively good. These new findings and results have established a theoretical and practical base for developing a new process for heap leaching of low grade gold ores in this system. And the new process owns a series of merits such as, non-cyanogens, nontoxic, broader applicability.

Jan 1, 2006

By J. N. Hryn, E. J. Daniels, M. Askew, Kirchner. G.

This presentation addresses the changing regulatory climate towards aluminum dross and salt cake in Europe and in the United States. Although sporadic, the trend in the U.S. continues to be away from command-and-control regulation of these materials. This trend began in the early 1980s when the Environmental Protection Agency was successfully sued in court and prevented from classifying dross as a hazardous material. The situation in Europe is different. Because of Council Directive 96/61/EC from the European Commission, European Union member countries have all passed legislation that will essentially cause all salt cake and drosses to be reprocessed. The implementation date of the legislation varies from country to country: from 2001 in the United Kingdom to 2007 in Germany, France, Austria, Italy, and Spain. The European aluminum industry is urging the EC to use the approach adopted by the U.S. EPA, which declassifies the majority of aluminum drosses and salt cakes.

Jan 1, 2000

By Sharon K. Young

What might an ideal leach-to-cathode/product system look like in the next century? The paper looks at the synergies of the 60&apos;s and 70&apos;s that led to the highly effective copper leach SX-EW system of the 90&apos;s. Standing in the year 2020 focuses on what breakthrough technologies might make possible a next generation leach/extraction/metal recovery system. Many of the pieces of such a technology have been developed, even piloted: in situ leaching, enhanced bioleaching, heap leaching of fine particles, resin in pulp, ion exchange, alternate anode reaction electrowinning, novel anode coatings. With nearly non-existent research on the part of individual large companies, the greatest challenge may not be inventing the technologies but rather inventing an industry "will to create."

Jan 1, 1999

By J. E. Dutrizac

A mineralogical study of a weak acid leach residue from the Clarksville zinc plant of Savage Zinc Inc. was carried out. The study focused on Pb and Cd as these elements most significantly impact on the environmentally acceptable disposal of the residue. The residue consists of major amounts of bassanite, zinc ferrite and various Zn-Pb-Fe-Cd silicate species. Also present are lesser quantities of PbSO4, sphalerite, Fe2O3 quartz, Mn-Pb-Fe oxides, SrS04, (Pb,Sr)SO4 iron gel-silica gel, jarosite and Ti oxide. The principal Cd carriers are the zinc ferrite, which contains up to 9.00% Cd and likely accounts for -45% of the total Cd content of the residue, and the various silicate species which contain up to 6.97% Cd and account for about 45 % of the total Cd. The sphalerite is a minor Cd carrier containing an average of 0.35 % Cd and accounting for -5 % of the total Cd; the other carriers contribute only trace amounts to the total Cd content. The major Pb carriers are PbS04, Pb-bearing silicates and Mn-Pb-Fe oxides. Minor proportions of the total 1.09% Pb content of the residue are carried by SrS04 and (pb,Sr)S04&apos; Trace Ph carriers include the iron gel-silica gel, Fe-Zn-AI oxide and bassanite. The residue after the toxicity characteristic leaching procedure (TCLP) is mineralogically very similar to the initial weak acid leach residue; the amounts of calcium sulphate are approximately the same in the two products. The principal Cd and Pb carriers are also the same as those noted in the initial residue, except that some dissolution and reprecipitation of Pb-Sr sulphate takes place. That the residue fails the TCLP test is likely a consequence of the superficial dissolution of Pb and Cd from species such as PbS04 or Zn-Pb-Fe-Cd silicate.

Jan 1, 1995

By Steven Wright

BHP Billiton?s Olympic Dam copper flash smelter employs the direct to blister process for smelting high grade copper concentrates. SO2 evolution during tapping gives rise to safety concerns. A thermodynamic model for the blister copper (Cu-Fe-S-O) was used to predict the volumes of SO2 evolved. The Multiple Phase Equilibria Model (MPE) was used to evaluate the slag chemistry inside the furnace. The blister copper model was used to explore the relationship between %S and %O in the copper and the amount of SO2 evolved on cooling. The volume of SO2 evolved was sensitive to the O content with reduction to levels below 0.2 ? 0.15% likely to suppress SO2evolution on cooling. Concentrations of S and O in copper samples from trials generally lay above the equilibrium line calculated for an average temperature of 1275C and a partial pressure of SO2 of 1 atm. Consequently there is a thermodynamic driving force for SO2evolution when cooling to this temperature during tapping. A number of potential process options to suppress SO2 evolution on tapping were investigated thermodynamically. Some of the options require treatment of the blister in a forehearth or separate furnace, while others impact on current practises in the flash furnace with slag present. The opportunities that these options present are discussed.

Jan 1, 2006

By E. Açma

In this study, the production of Cu, Co, and magnetic iron oxide from the ancient copper, slags, located in Küre-Turkey, is investigated. In the process under development, fayalitic slags containing 1% Cu, 0.43% Co are reduced in a D.C. arc furnace with coke or graphite additions. A metallic alloy, consisting of 3.8% Cu, 3.3% Co, 2.1% S, and the rest being Ice, is produced by granulation of the liquid metal. About 85% recoveries of Cu and C:o are achieved by hot sulfuric acid leaching of these granules followed by H2S precipitation. The, production of magnetic iron oxide is possible from the discarded leach solution, loaded v:ith FeS04, by using a method with geothite precipitation, dehydration, controlled reduction, and re-oxidation steps. The magnetic oxides produced have 20 m2Jg surface area, 1:8.3 aspect ratio, and the coercivity of 330-380 Oersted.

Jan 1, 1993

By Guy L. Fredrickson

A modified transpiration reactor was used to measure the composition of the equilibrium gas phase formed above compounds in the Hg-O-S system at high temperatures (600 to 900K). A thermodynamic database {(AGo°f AH°t. AS°t)} for-HgO, HgS, HgSO4, Hg2SO4, HgSO4?HgO, and HgSO4?2HgO was developed based on the experimental results. Prior to this study, only estimated data were available in the literature for the sulfates and oxysulfates at temperatures above 298K. A series of vapor pressure&apos; stability diagrams were constructed from 473 to 973K with isobars of Hg(g), HgO(g), S2(g), and SO3(g). These diagrams were found to be significantly different than those available previously and do provide insight to the phase relations of importance during the thermal processing of Hg-containing wastes. The thermodynamic results were used to conduct a series of Gibbs energy minimization calculations for a thermal processor&apos; afterburner system for the treatment of HgS-containing wastes. The retention of Hg in the discharge calcine was examined as a function of temperature and excess air. Hg was found to report to the calcine as HgSO4, Hg2SO4, or HgSO4 HgO depending on the process conditions, and Hg retention occurs at temperatures as high as 930K. The precipitation of Hg-containing phases from cooled afterburner discharge gas starts at approximately 900K and the cooling of the gas an additional 30K (to 870K) results in over 50% of the Hg being preCipitated as HgS04?HgO. It was also determined that for small amounts of Hg present in sulfide concentrates during roasting, the Hg will be retained as HgSO4 or HgSO4?HgO at temperatures as high as 870K.

Jan 1, 1996