Interactions between iron oxides and the additives olivine, quartzite and calcite in magnetite pellets

Abstract: In the present study, magnetite pellets with the additives olivine, calcite and quartzite were isothermally reduced in a tubular furnace to study the interaction between iron oxides and the additives. Exaggerated amounts of additives were used in order to enable analyses of phases that do not otherwise occur in sufficient amounts for X-ray diffraction and EDS-analyses. The reduction was set to yield either magnetite or wüstite in the temperature range 500-1300ºC. For olivine, reduction tests were also performed to allow metallization in the range 1000-1300ºC. The mineralogical phases which had formed were studied after oxidation as well as after reduction. The results showed that it was possible to identify, by X-ray diffraction, the main phases formed by the additives in all samples, after oxidation as well as reduction.In the olivine sample, the forsteritic olivine particles react partly during the oxidation pre-treatment to form magnesioferrite and vitreous silica along the particle corona. This breakdown of the olivine particles during oxidation liberates magnesium from the particles, which do not react until temperatures of above 1150°C in reducing atmosphere. When the hematite in the sample is reduced, and when temperature is high enough to allow solid-state diffusion at ~800ºC, the magnesium of the magnesioferrite redistributes so that the magnesium concentration approaches the same level throughout the structure. For magnetite, this does not occur below 800°C. At 1000°C, this magnesium reacts further with the silica in the glassy slag phase, which crystallizes into fayalitic olivine. At this temperature the magnesium diffuses over distances more than 600µm from the olivine particles. From this point the binding media to resist the swelling tensions in the pellet is mainly solid fayalite. The metallization front concentrates the MgO in the remaining wustite which can lead to MgO levels of up to 10% locally. The melting point of the fayalite is raised from 1145ºC to a melting range of 1238-1264ºC due to the MgO-increase, as estimated based on the phase diagram tuned to the pellets tested. Much of the olivine which remained unaltered in the oxidation process will be encapsulated by iron before the magnesium begin to dissolve in reducing conditions, and therefore play no role in the reduction before final melting of the particles occur.The quartzite particles are not affected by the oxidation pre-treatment. The binding strength of quartzite pellets therefore comes from the sintering of quartzite particles to neighboring hematite as well as the glassy slag resulting from the acid gangue and the bentonite. Substantial reaction of the quartzite particles during reduction did not occur before 1000ºC even though the process has occurred to a very low extent already at 900ºC. Also the glassy slag crystallizes into fayalite in the presence of quartzite. From this point fayalite represents the binding media in the pellet. Pure fayalite melts already at 1177ºC and can at this temperature dissolve up to 76wt% FeO. This leads to early softening, which is one of the main concerns for the softening/melting properties of the pellet. In the pellets with calcite, CaO reacts with Fe2O3 during induration to form a low-melting calcium ferrite slag in the pellet that melts to react with silica in the pellets. If more calcium is added than what is required to react with the silica, calciumferrites becomes part of the binding mass together with the dicalciumsilicate. The calciumferrites forming in pellets with larger additions of calcite are weak to resist the tensions arising due to the low-temperature reduction of hematite and are associated with low temperature disintegration. As the reduction proceeds to wustite, the calcium from the ferrite dissolves in the wustite so that porous calciumwustite forms. The dicalciumsilicate remain stable during the entire reduction until reaction and melting of the phase begin at 1283ºC.