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By Florian Kongoli

While calcium ferrite slags have been successfully used in continuous copper converting for the last 30 years, ferrous calcium silicate slag was proposed about 8 years ago as an additional alternative for copper smelting. Although both slags are normal extensions of each other their phase relations have not been completely clarified. In this paper the liquidus relations of both slags have been quantified at various areas that cover both of them. The existing experimental data have been first reviewed and discussed in relation to the solidification procedure. An original physical model is then used to predict various diagrams of the liquidus surface of both slags. It is shown that the ternary liquidus diagrams normally used for FeOx-SiO2-CaO system are not suitable for industrial slags. The new model diagrams of Fe/CaO versus SiO2 and Fe/SiO2 versus CaO as well as Fe/CaO versus Temperature and Fe/SiO2 versus temperature are proven to be much more convenient for ferrite and ferrous calcium silicate slags. Based on these diagrams the effect of SiO2 and CaO on the melting temperature is quantified. The effect of Cu2O is also quantified through the model. Some Fe/CaO versus Cu2O and Fe/SiO2 versus CaO at various copper contents are predicted and the results show good agreement with the experimental data. It is also shown that in the presence of liquid copper, Cu2O is dissolved in the slag depending on the oxidation degree of the system and might lower the liquidus temperature. Some discussions are also presented taking into account plant observations and important conclusions are drawn for copper smelting and converting

Jan 1, 2006

By J. M. Demarthe

MINEMET RECHERCHE (IMETAL Group, formerly Le Nickel-Penarroya-Mokta) has studied on a laboratory scale and patented a new process to recover metal values -copper- from sulphide ores and concentrates. It combines a cupric leaching, solvent extraction and copper sulphate electrowinning according to the main following steps - A direct and selective leaching of copper sulphide ores or concentrates at atmospheric pressure with cupric chloride to form cuprous and ferrous chlorides and elemental sulphur. Pyrite remains in the sulphur residue. - The leach solution is separated into two parts -In the first one, air is injected to precipitate iron as goethite. The oxidation step can be easily realized at atmospheric pressure by maintaining an excess of cuprous and-ferrous chlorides in the liquor. Copper is extracted from the second part as cupric ion by an LIX reagent. Direct injection or air in the mixing chamber maintains good extraction conditions, so that only one mixer settler is required. - Iron, in the form of ferrous ion, is not coextracted. - Copper is stripped from the organic phase, transferred into a sulfuric phase and sent to sulphate electrowinning cells, which are now conventional in copper metallurgy. - Only electricity and air are required. After a feasibility study, the next step will be to develop it on a pilot and commercial scale.

Jan 1, 1976

By Florian Kongoli

While calcium ferrite slags have been successfully used in continuous copper converting for the last 30 years, ferrous calcium silicate slag was proposed about 8 years ago as an additional alternative for copper smelting. Although both slags are normal extensions of each other their phase relations have not been completely clarified. In this paper the liquidus relations of both slags have been quantified at various areas that cover both of them. The existing experimental data have been first reviewed and discussed in relation to the solidification procedure. An original physical model is then used to predict various diagrams of the liquidus surface of both slags. It is shown that the ternary liquidus diagrams normally used for FeOx-SiO2-CaO system are not suitable for industrial slags. The new model diagrams of Fe/CaO versus SiO2 and Fe/SiO2 versus CaO as well as Fe/CaO versus Temperature and Fe/SiO2 versus temperature are proven to be much more convenient for ferrite and ferrous calcium silicate slags. Based on these diagrams the effect of SiO2 and CaO on the melting temperature is quantified. The effect of Cu2O is also quantified through the model. Some Fe/CaO versus Cu2O and Fe/SiO2versus CaO at various copper contents are predicted and the results show good agreement with the experimental data. It is also shown that in the presence of liquid copper, Cu2O is dissolved in the slag depending on the oxidation degree of the system and might lower the liquidus temperature. Some discussions are also presented taking into account plant observations and important conclusions are drawn for copper smelting and converting

Jan 1, 2006

By Sayan Sarkar

HAMR (Hydrogen Assisted Magnesiothermic Reduction) process is a promising alternative route of titanium production, which is convenient due to reduction at relatively lower temperatures below 750 °C and usage of cost-efficient TiO2 as the starting material. A crucial step involved in this process requires the Mg reduction of TiO2 subjected to H2 atmosphere which produces porous TiH2 along with residual magnesium impurities. Before the final heat treatment and deoxygenation steps for consolidation of the Ti powder, leaching plays a significant role in the removal of Mg impurities. In this report, we present a systematic study on the role of acid concentration (HCl), temperature and the kinetics of MgO dissolution. In addition, we also report the controlling mechanism during kinetics of MgO dissolution in acid. This parametric study will provide a platform to ensure very low Mg content that meets with ASTM standards during production of Ti in the HAMR process.

By T. Wang, R. G. Reddy, D. Mantha

"A new eutectic LiN03-NaN03-KN03-KN02 quaternary molten salt system was calculated using thermodynamic modeling. The eutectic temperature was predicted to be 100°C. The melting point and heat capacity of the salt eutectic composition were determined using DSC. The experimentally determined melting point is in excellent agreement with the predicted value. The melting point is more than 124°C lower than that of the KN03-NaN03 solar salt. The density of the molten salt was experimentally determined as function of temperature. Using the density, heat capacity and the melting point, thermal energy storage density and gravimetric storage density of the quaternary molten salt were calculated and compared with that of solar salt. The larger storage density value of this molten salt indicates that this salt has a better energy storage capacity for solar power generation systems.IntroductionMolten salts have been used as thermal energy storage media for solar energy applications. Nitrates are being used in the solar energy applications for their low melting point, low unit cost, high heat capacity, high thermal stability, negligible vapor pressure and high energy storage density [l]. Solar salt (NaN03/KN03: 60/40) is the most popular thermal energy storage medium which is currently being used with the freezing point of 221 ·c [2]; another ternary system HITEC® which contains NaN03, KN03 and NaN02 has freezing point of 141°C [3]. Newer nitrate salt mixtures are being studied and projected as potential candidates for thermal energy storage (TES) and heat transfer (HT) applications. Based on these favorable features, molten salt can work directly as the energy storage medium below 500°C [l]. Development and synthesis of newer molten salt mixtures with freezing point lower than those currently used for thermal energy storage applications is necessary for sustained utilization of solar energy. The approach to develop lower freezing point molten salt mixtures is by the prediction of new eutectic mixtures and also by the development of new nitrate compounds."

Jan 1, 2012

By Matti Hämäläinen

Outokumpu has developed a new chloride leaching process, HydroCopper?, for copper concentrates. The process utilizes the cupric ion as oxidant, which is able to dissolve chalcopyrite. After solution purification monovalent copper is precipitated as cuprous oxide, Cu2O, using sodium hydroxide. Copper product is produced from Cu2O by reduction, melting and casting. An essential part of the new process is chlor-alkali electrolysis, which regenerates the reagents used. All impurity metals are removed before Cu2O precipitation, because otherwise they would report to the copper product, impairing its quality. A multistage solution purification scheme has been developed consisting of firstly, chemical precipitation of impurity metals by pH increase, secondly, cementation of silver and thirdly, removal of trace multivalent ions using ion exchange. This paper describes the characteristics of solution purification in the HydroCopper? process based on the laboratory tests and pilot runs made by Outokumpu Research Oy.

Jan 1, 2003

By John R. Goode

The fist part of this paper comprises a general discussion on refractory gold ores and their mineralogy. Processing methods now in use are reviewed and test procedures for the important methods are discussed. Factors determining the selection of a process are outlined. The paper includes a survey of production plants using pressure oxidation, roasting and biological oxidation to process refractory ore. The status of processes under development is briefly reviewed.

Jan 1, 1993

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 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.

By George Kazonich

The high costs and environmental problems associated with making iron and steel in the United States is driving the development of new technologies to replace the blast furnace. A prototype reactor incorporating rocket technology was designed and built. This rapid rate reactor was operated successfully and consistently made iron metal. Minus 325-mesh magnetite particles could be reduced to iron metal in less than 50 ms in a high temperature flow through reactor. Iron product was recovered inside the reactor and in a downstream cyclonic separator. The results of typical operation and how parametric changes affected the reduction of iron ore concentrates are discussed.

Jan 1, 1993

By Brian Patrick, Norman Bell, Mark Schoenfield, Thomas Weber, Dietrich Gross

"The reduction of carbon dioxide emissions and the resultant greenhouse gas affect is hampered by the fact that all fossil fuels contain copious quantities of carbon. Process tweaking can keep the amount of carbon dioxide to a minimum but cannot significantly reduce the amount of carbon dioxide generated. The very nature of utilizing fuels requires that they be burned to release the heat required for the various processes. Reduction of metal oxides to manufacture or modify pure metals, generation of power, transportation and many other forms of fuel usage result in much of the generation of man made carbon dioxide. Oxyfuel is a unique contributor to carbon dioxide emissions. While creating higher concentrations of carbon dioxide the total volume of carbon dioxide generated is reduced. This paper will examine the unique characteristics and potential of oxyfuel that make the generation of lower volumes of carbon dioxide possible.Nearly ten years ago a commercial application of oxy-fuel was installed at Jupiter Aluminum Company in Hammond, Indiana. This process was funded and developed by Dietrich Gross CEO. This aluminum remelt facility now runs completely on oxy-fuel and has continuously for over ten years. This has reduced the melt rates to as low as 750 BTU per pound in continuous melting periods."

Jan 1, 2009

By Kota Nakashima

Residues from titanium smelting tend to contain scandium. The scandiumis discarded because no suitable process exists for its recovery from the residue. Valuable-metal recovery from discharged residue is critical for environmental conservation and to achieve a sustainable society. Since 2015, JXNippon Mining&Metals has been developing a process for scandium recovery from the residue of a titaniumsmelting process. The process consists of the following steps: scandium concentrating by classification or neutralization, selective scandium leaching, impurity removal by neutralization, solvent extraction of scandium by using D2EHPA, purification, and roasting. We optimized the above steps to achieve an effective process to obtain scandium oxide (Sc2O3). In this paper, we introduce results from the bench-scale test of the scandium recovery flowsheet developed by JX Nippon Mining & Metals.

Hazardous waste has often very complicated chemical compositions in a variety of physical forms and is normally processed in rotary kiln incinerators. Due to large variations in waste types and difficulties in feed characterization, the complex transport processes within the incinerator are not well understood, and the incineration process meets challenges in a smooth operation, and expects various uncertainties in the process chemistry and emission control. For better understanding of the incineration process, simulation was carried out by using Computational Fluid-dynamics (CFD) to characterize temperature and species distribution in the incinerator. In order to catch certain aspects of thermal and chemical behavior, a novel approach is proposed to represent approximately the waste streams and the subsequent combustion process. Hazardous waste in various forms from an industrial-rotary-kiln waste incinerator is firstly converted to a hydrocarbon-based virtual fuel mixture with approximately the same HIC molar ratio and calorific value. The simulation of the combustion process of the simplified hazardous waste was proceeded with a combustion model. The distribution of temperature and chemical species especially the remaining CO in the system is preliminarily investigated. Distribution of CO concentration, as a good indicator of emission level for the incineration process, could be used to evaluate the emission control. The predicted temperature distribution has been compared with available measurement data from an operating rotary kiln waste incinerator at A VR-Chieme, in the Netherlands. Reasonable agreement has been reached between the measured and predicted temperature data. [n the next step, measurement of species distribution in the system is planned to further validate the combustion model.

Jan 1, 2003

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 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' 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' 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

By R. G. Reddy

The effect of solid particles on viscosity behavior of Na2O-O-B2O3-SiO2 melts of composition XSio2/XNa2o =0.5 and in the temperature range of 900- 1150 K was studied. Samples were analyzed by X-ray diffraction and optical microscopy. The results showed that a crystalline phase (NaBO2) was formed and its amount increases with decrease in X,, from 0.50 to 0.25. The experimental viscosity values were compared with the predicted values using our viscosity model developed earlier. At low temperatures, for low content of B2O3 , the experimental values exhibits a large deviation from the predicted values. It was concluded that the deviation was due to the formation of solid particles in the molten slags. The existence of these solid particles increased the viscosity values significantly. A new viscosity model was developed to include the effect of solid particles.

Jan 1, 1993

By Tiejun Chun, Jian Pan, Deqing Zhu, Zhiyong Ruan

"In this paper, the desulfuration of pyrite cinder pellets was carried out. Phase analysis shows that most sulfur of pyrite cinder exists in the form of elementary sulfur. Most sulfur was removed in preheating stage. 81.25% sulfur was removed and the average SO2 concentration of exhaust gas was 1365ppm when the pellets were preheated at 950oC for 9 min. The final product, assaying 62.42wt%Fe and 0.02wt%S content at 96.88% desulfuration was achieved under the conditions of preheating at 950? for 9 min and roasting at 1200? for 15 min, which can be used as the burden for blast furnace.IntroductionPyrite cinder, as a subsidiary product of sulfuric acid production by roasting of pyrite ores, was solid waste in sulfuric acid enterprises. According to the statistics, the annual production of pyrite cinder is about 15 million tons in China. Besides, there is lots of pyrite cinder deposited for many years [1-3]. The pyrite cinder consumed in the cement and other industries as auxiliary additives only accounts for less 30% of its total discharge and the left is stored in waste pond, occupying much land and polluting environment in China [4-5]. Moreover, pyrite cinder contains iron between 30-63% which can be utilized as a cheap raw material for ironmaking by sintering or pelletizing processes, which can not only prevent pollution but also provide cheap raw materials for ironmaking [6-7]. However, compared to traditional iron ore concentrate, pyrite cinder possesses higher sulfur content."

Jan 1, 2012

By Salustio s. Guzman

The standard .free energies of formation of tin chlorides were estimated with reviewed and estimated basic thermodynamic data, and measured reversible potentials for the disproportionation of tin dichloride into metallic tin and tin tetrachloride. Values for cºp, Sº, Hº?-Hº 298, -(Gº - Hº298) /T,.Hºf, Gºf, and log Kp are given in tabular form, these estimations are compared with estimations reported in the literature.

Jan 1, 1985

By D. McConchie

Management of caustic red mud wastes at the QAL bauxite refinery uses an innovative approach . involving neutralising the red mud with seawater; solids settle in a Red Mud Dam and residual water (pH = 8.6) is discharged to a tidal inlet. A survey of 18 trace elements in sediment, water, mangroves and molluscs, and an ecological survey of benthic fauna in the inlet, and at near-pristine control sites, revealed no significant trends that were linked to the discharge, except for the concentration of Al which was slightly elevated within 100m of the outfall. Trace element concentrations in water samples were close to, or below, world average seawater values and oysters collected near the outfall were acceptable for human consumption. The impact of discharges is minimised by a high tidal range, >60% flushing of the inlet in each tidal cycle, and the very high trace element binding capacity of sediment in the dam (> 100meq/ 100g dry mud).

Jan 1, 1996

By Jose Castro

The growing demand of scrap to supply the electric arc furnace has driven to search for new alternatives of raw material. The DRI produced using self-reducing pellets has become competitive due to the potential use of a wide range of carbonaceous materials such as coal, charcoal, biomass etc. In this context, the rotary kiln process using improved technologies such as post-combustion and self-reducing burden is a promising source of high quality raw materials. This paper presents a mathematical model of the rotary kiln process designed for self-reducing pellets and post-combustion. The model is based on the transport equation of two-phase flow, energy and mass transfer. The solid material is composed of a typical self-reducing pellet. The model considers the solid phase (C, volatiles, Fe2O3, Fe3O4, FeO, Fe, H2O, SiO2, Al2O3, MgO, P2O5, K2O, Na2O, FeS, CaO and gangue) and the gas phase (N2, O2, CO, CO2, H2, H2O, SO, SO2 and SiO). For each of the above components a conservation equation is solved and the mass and energy transport is accounted. The set of differential equations are coupled by the rate equations describing the kinetics of the several reactions, which take place within the rotary kiln. All the conservation equations are solved based on the finite volume method applied for a three-dimensional cylindrical coordinate system. Simulation results are presented for global parameters such as metallization degree, productivity, gas utilization ratio and calorific value. Inner conditions such as three-dimensional gas and solid temperature patter and compositions are discussed.

Jan 1, 2006