In the present study, the corrosion behaviour of several magnesia-chrome (MC) and magnesia-alumina spinel (MA) bricks against fayalite type slags was investigated and the role of the spinel phases was highlighted . The experimental results revealed that the corrosion resistance of the MC bricks was superior to the MA bricks against KIVCET slags in static and dynamic conditions . As a result of the interaction between MgO from MC bricks and the slag, a modified forsterite phase (Mg, Fe, Zn, Ca)₂SiO₄ was formed, which destroyed the precipitated complex spinel bonds at the grain boundaries of periclase and magnesia-chromia spinel . Furthermore, both MgO and MgO-MgAl₂O₄ spinel in the MA brick dissolved into the slag, which resulted in modified forsterite phases of (Mg, Fe, Zn, Ca)₂SiO₄ and (Mg, Fe, Zn)(Fe, Al)₂O₄ complex spinels, respectively. In addition, the accretion formation in the KIVCET furnace was investigated through solubility experiments of Cr₂0₃ in the KIVCET slag with various amounts of lead, which revealed that the net contribution of Cr₂0₃ to the spinel formation is the highest in the barren (no Pb) slag, followed by high-lead (11% Pb) and it is the lowest for the low-lead (6% Pb) slag. The amount of spinel solid solution increased consistently with increasing Cr₂0₃ dissolved and the PbO existent in the slag. From examinations of several used bricks from the tuyere area of a Peirce Smith nickel converter, it was found that the corrosion is due to the interaction of the partially oxidized matte penetrating deep into the brick and the magnesia grains forming (Mg, Fe, Ni, Co) xOy spinels . Analyses of brick samples used in the KIVCET Electric Furnace roof identified deep reaching sulphation, which weakened the bonding phase between coarse magnesia grains. In the Bottom Blown Oxygen Converter, a highly aggressive lead and bismuth oxide rich slag penetrated deep into the brick, which destroyed the grain boundaries, causing the refractory to be easily eroded at the refractory-slag interface. Our studies concluded that the spinel phases, either as magnesium chromate, magnesium aluminate or complex spinel [(Mg, Fe)(Cr, Al, Fe)₂O₄], enhanced the corrosion resistance of a basic refractory to fayalite type slags from the non-ferrous smelting and converting furnaces.

In the present study, the corrosion behaviour of several magnesia-chrome (MC) and magnesia-alumina spinel (MA) bricks against fayalite type slags was investigated and the role of the spinel phases was highlighted . The experimental results revealed that the corrosion resistance of the MC bricks was superior to the MA bricks against KIVCET slags in static and dynamic conditions . As a result of the interaction between MgO from MC bricks and the slag, a modified forsterite phase (Mg, Fe, Zn, Ca)₂SiO₄ was formed, which destroyed the precipitated complex spinel bonds at the grain boundaries of periclase and magnesia-chromia spinel . Furthermore, both MgO and MgO-MgAl₂O₄ spinel in the MA brick dissolved into the slag, which resulted in modified forsterite phases of (Mg, Fe, Zn, Ca)₂SiO₄ and (Mg, Fe, Zn)(Fe, Al)₂O₄ complex spinels, respectively. In addition, the accretion formation in the KIVCET furnace was investigated through solubility experiments of Cr₂0₃ in the KIVCET slag with various amounts of lead, which revealed that the net contribution of Cr₂0₃ to the spinel formation is the highest in the barren (no Pb) slag, followed by high-lead (11% Pb) and it is the lowest for the low-lead (6% Pb) slag. The amount of spinel solid solution increased consistently with increasing Cr₂0₃ dissolved and the PbO existent in the slag. From examinations of several used bricks from the tuyere area of a Peirce Smith nickel converter, it was found that the corrosion is due to the interaction of the partially oxidized matte penetrating deep into the brick and the magnesia grains forming (Mg, Fe, Ni, Co) xOy spinels . Analyses of brick samples used in the KIVCET Electric Furnace roof identified deep reaching sulphation, which weakened the bonding phase between coarse magnesia grains. In the Bottom Blown Oxygen Converter, a highly aggressive lead and bismuth oxide rich slag penetrated deep into the brick, which destroyed the grain boundaries, causing the refractory to be easily eroded at the refractory-slag interface. Our studies concluded that the spinel phases, either as magnesium chromate, magnesium aluminate or complex spinel [(Mg, Fe)(Cr, Al, Fe)₂O₄], enhanced the corrosion resistance of a basic refractory to fayalite type slags from the non-ferrous smelting and converting furnaces.

In the present study, the corrosion behaviour of several magnesia-chrome (MC) and magnesia-alumina spinel (MA) bricks against fayalite type slags was investigated and the role of the spinel phases was highlighted . The experimental results revealed that the corrosion resistance of the MC bricks was superior to the MA bricks against KIVCET slags in static and dynamic conditions . As a result of the interaction between MgO from MC bricks and the slag, a modified forsterite phase (Mg, Fe, Zn, Ca)₂SiO₄ was formed, which destroyed the precipitated complex spinel bonds at the grain boundaries of periclase and magnesia-chromia spinel . Furthermore, both MgO and MgO-MgAl₂O₄ spinel in the MA brick dissolved into the slag, which resulted in modified forsterite phases of (Mg, Fe, Zn, Ca)₂SiO₄ and (Mg, Fe, Zn)(Fe, Al)₂O₄ complex spinels, respectively. In addition, the accretion formation in the KIVCET furnace was investigated through solubility experiments of Cr₂0₃ in the KIVCET slag with various amounts of lead, which revealed that the net contribution of Cr₂0₃ to the spinel formation is the highest in the barren (no Pb) slag, followed by high-lead (11% Pb) and it is the lowest for the low-lead (6% Pb) slag. The amount of spinel solid solution increased consistently with increasing Cr₂0₃ dissolved and the PbO existent in the slag. From examinations of several used bricks from the tuyere area of a Peirce Smith nickel converter, it was found that the corrosion is due to the interaction of the partially oxidized matte penetrating deep into the brick and the magnesia grains forming (Mg, Fe, Ni, Co) xOy spinels . Analyses of brick samples used in the KIVCET Electric Furnace roof identified deep reaching sulphation, which weakened the bonding phase between coarse magnesia grains. In the Bottom Blown Oxygen Converter, a highly aggressive lead and bismuth oxide rich slag penetrated deep into the brick, which destroyed the grain boundaries, causing the refractory to be easily eroded at the refractory-slag interface. Our studies concluded that the spinel phases, either as magnesium chromate, magnesium aluminate or complex spinel [(Mg, Fe)(Cr, Al, Fe)₂O₄], enhanced the corrosion resistance of a basic refractory to fayalite type slags from the non-ferrous smelting and converting furnaces. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

In the production of base metals by smelting of sulphide ore concentrates, large amounts of iron are rejected with iron silicate slags. These slags contain Ni, Cu and Co in concentrations up to several percent units. Extraction of the entrapped base metals using high pressure oxidative acid leaching (HPOXAL) was investigated in this work. Crystalline slags containing fayalite (Fe2SiO4), magnetite (Fe3O4), silica (SiO2) and matte (MeSn<1) were found to be highly amenable to leaching at 250°C, 90 psi (6.2 bar) O2 partial pressure and 70 g/L initial H2SO4. Extractions of Ni, Co and Cu exceeded 90% within 15-20 min and arrived at 95-97% after 45 min. The residues of leaching were identified as aggregates of crystalline hematite (Fe2O3) and amorphous silica. Dissolution of fayalite and magnetite was shown to be acid driven. Since HPOXAL operates with substoichiometric additions of sulphuric acid (10-20% of the stoichiometric requirement), acid regeneration facilitated by iron oxidation and hydrolysis is crucial to high rates of leaching. Low acidities (<10 g/L) were shown to cause precipitation of ferrous sulphate, slowing acid regeneration and slag dissolution. Elevated acidities (>70 g/L) result in excessive concentrations of Fe(III) in the leach solution, complicating downstream processing. The use of pyrrhotite tailings, an environmentally hazardous waste, as a substitute of sulphuric acid in slag leaching was investigated. Oxidative co-leaching of pyrrhotite tailings with naturally cooled converter slag at 250°C, 90 psi (6.2 bar) O2, 68 g/L equivalent H2SO4 was shown to have kinetics comparable to adding sulphuric acid with final extractions reaching 95-97% in 45 min. Granulation of slag melt can produce an amorphous solid solution of SiO2 and metal oxides. Amorphous slag is not amenable to HPOXAL due to the formation of a passive layer of silica. Leaching of amorphous slag at low temperatures was shown to proceed nearly to completion. The difference in the leachability of amorphous slag at high and low temperatures is explained in terms of the rate of silicic acid re-polymerization leading to closure of pores in the leached layer.

In the production of base metals by smelting of sulphide ore concentrates, large amounts of iron are rejected with iron silicate slags. These slags contain Ni, Cu and Co in concentrations up to several percent units. Extraction of the entrapped base metals using high pressure oxidative acid leaching (HPOXAL) was investigated in this work. Crystalline slags containing fayalite (Fe2SiO4), magnetite (Fe3O4), silica (SiO2) and matte (MeSn<1) were found to be highly amenable to leaching at 250°C, 90 psi (6.2 bar) O2 partial pressure and 70 g/L initial H2SO4. Extractions of Ni, Co and Cu exceeded 90% within 15-20 min and arrived at 95-97% after 45 min. The residues of leaching were identified as aggregates of crystalline hematite (Fe2O3) and amorphous silica. Dissolution of fayalite and magnetite was shown to be acid driven. Since HPOXAL operates with substoichiometric additions of sulphuric acid (10-20% of the stoichiometric requirement), acid regeneration facilitated by iron oxidation and hydrolysis is crucial to high rates of leaching. Low acidities (<10 g/L) were shown to cause precipitation of ferrous sulphate, slowing acid regeneration and slag dissolution. Elevated acidities (>70 g/L) result in excessive concentrations of Fe(III) in the leach solution, complicating downstream processing. The use of pyrrhotite tailings, an environmentally hazardous waste, as a substitute of sulphuric acid in slag leaching was investigated. Oxidative co-leaching of pyrrhotite tailings with naturally cooled converter slag at 250°C, 90 psi (6.2 bar) O2, 68 g/L equivalent H2SO4 was shown to have kinetics comparable to adding sulphuric acid with final extractions reaching 95-97% in 45 min. Granulation of slag melt can produce an amorphous solid solution of SiO2 and metal oxides. Amorphous slag is not amenable to HPOXAL due to the formation of a passive layer of silica. Leaching of amorphous slag at low temperatures was shown to proceed nearly to completion. The difference in the leachability of amorphous slag at high and low temperatures is explained in terms of the rate of silicic acid re-polymerization leading to closure of pores in the leached layer.

During the pyrometallurgical extraction of copper, a significant part of the copper is lost with discard slag, which decreases profits, overall copper recovery, and efficiency of raw material usage. Smelting furnace slag usually has a copper content that is close to or higher than that of copper ores. The investigation of copper losses to slag is thus a task of practical significance, as the ore grades are depleting. Slag cleaning, e.g., a settling furnace, can reduce copper losses to slag as the mechanically suspended copper-containing droplets separate from slag under the action of gravity and can hence be recovered.  An industrial trial was conducted in an electric settling furnace with slag originating from an electric smelting furnace and processed in a zinc fuming furnace. The trial was conducted to increase the understanding of copper losses to slag and how the process parameters temperature and settling time influence the slag copper content. The obtained slag samples were also evaluated to gain better insights as to the settling mechanism and, if any, factors that hinder the copper phases from settling. Slag modification with CaO was also evaluated to investigate how the modification influences the settling of copper phases and, thus, the final slag copper content.  Samples collected during the industrial trial were the basis for the evaluation in the current work. The samples came from batches with varying temperatures, settling times, and CaO content collected at four different sample positions. Instrumental techniques, including XRF, FAAS, ICP-SFMS, and SEM-EDS, were used to analyze the chemical compositions of the samples and the appearance of copper and associated phases.  The results indicated that the copper content of outgoing slag increased with increasing temperature in the evaluated interval. The copper content was also concluded to be more strongly affected by the temperature compared to the settling time. Regulating the temperature to the lower temperature interval in the settling furnace could thus decrease the final slag copper content. During the slag characterization, it was found that suspended copper-containing phases were hindered from settling, due to the attachment to solid phases and gas bubbles in the slag. By controlling and minimizing the presence of the bottom buildup and thus solid phases in the slag, the copper content can be decreased. The results indicated that the CaO slag modification decreased the final slag copper content, and can thus be used as a modifier for increased settling.