Metallurgical grade alumina is produced worldwide through the well-known Bayer process, which unavoidably generates bauxite residue (BR, also known as red mud) in almost equal amounts to alumina. This study aims the valorization of BR through a smelting-reduction process to obtain calcium aluminate slags that can be a proper feed for alumina recovery via the Pedersen process. It investigates the thermodynamics and characteristics of the slags and pig iron produced from mixtures of BR, a bauxite beneficiation byproduct, and lime. In this context, the evolution of the different phases in the slags is studied with advanced analytical techniques and thermodynamic calculations. According to the results, a CaO/Al2O3 mass ratio within 1.3 to 1.4 in the slags can yield more Al2O3-containing leachable phases, such as CaO·Al2O3 and 12CaO·7Al2O3. The cooling dictates the amount and the characteristics of these phases, and the slower cooling rate yields improved slag characteristics. The distribution of the elements between the slag and metal phases shows that iron is separated, and the majority of the P, Cr, Ni, and V are distributed in the produced pig iron, while S, Ti, and Si are mostly concentrated in the slags.
The aluminothermic reduction process of manganese oxide from different slags by aluminum was investigated using pure Al and two types of industrial Al dross. Two types of MnO-containing slags were used: a synthetic highly pure CaO-MnO slag and an industrial high carbon ferromanganese slag. Mixtures of Al and slag with more Al than the stoichiometry were heated and interacted in an induction furnace up to 1873 K, yielding molten metal and slag products. The characterization of the produced metal and slag phases indicated that the complete reduction of MnO occurs via the aluminothermic process. Moreover, as the Al content in the charge was high, it also completely reduced SiO2 in the industrial ferromanganese slag. A small mass transport of Ca and Mg into the metal phase was also observed, which was shown to be affected by the slag chemistry. The obtained results indicated that the valorization of both Al dross and FeMn slag in a single process for the production of Mn, Mn-Al, and Mn-Al-Si alloys is possible. Moreover, the energy balance for the process indicated that the energy consumption of the process to produce Mn-Al alloys via the proposed process is insignificant due to the highly exothermic reactions at high temperatures.
Hydrogen and aluminum were used to produce manganese, aluminum–manganese (AlMn) and ferromanganese (FeMn) alloys through experimental work, and mass and energy balances. Oxide pellets were made from Mn oxide and CaO powder, followed by pre-reduction by hydrogen. The reduced MnO pellets were then smelted and reduced at elevated temperatures through CaO flux and Al reductant addition, yielding metallic Mn. Changing the amount of the added Al for the aluminothermic reduction, with or without iron addition led to the production of Mn metal, AlMn alloy and FeMn alloy. Mass and energy balances were carried out for three scenarios to produce these metal products with feasible material flows. An integrated process with three main steps is introduced; a pre-reduction unit to pre-reduce Mn ore, a smelting-aluminothermic reduction unit to produce metals from the pre-reduced ore, and a gas treatment unit to do heat recovery and hydrogen looping from the pre-reduction process gas. It is shown that the process is sustainable regarding the valorization of industrial waste and the energy consumptions for Mn and its alloys production via this process are lower than current commercial processes. Ferromanganese production by this process will prevent the emission of about 1.5 t CO2/t metal.
Fe-26.38Si-9.35B eutectic alloy is proposed as a phase change material (PCM) as it exhibits high latent heat, high thermal conductivity, moderate melting point, and low cost. For successful implementation of it in the latent heat thermal energy storage (LHTES) systems, we investigate the use of graphite as a refractory material that withstands long-term melting/solidification in contact with the Fe-26.38Si-9.35B alloy. The PCM has been thermally cycled up to 1–4 times below and above its melting point at the temperature interval of 20 °C or 100 °C. It is observed that this eutectic alloy shows good thermal stability over a small temperature range of 1057–1257 °C. Some SiC and B4C solid precipitation will be formed at the top of the alloy. However, it does not seem to increase with time. The graphite crucible as a refractory material will produce a protective layer of SiC and B4C that will hinder the interaction between the PCM and the crucible. The small volume change during solidification will not break the graphite crucible during cycling. The chemical wear or dissolution of the crucible is negligible. It demonstrates the viability of Fe-26.38Si-9.35B alloy as a heat storage material in this type of container.
The hydrogen reduction of bauxite residue lime pellets at elevated temperatures was carried out to recover iron and alumina from the bauxite residue in a new process route. Prior to the H2 reduction, oxide pellets were initially prepared via the mixing of an industrial bauxite residue with fine calcite powder followed by calcination and high-temperature sintering. The chemical, compositional, and microstructural properties of both oxide and reduced pellets were studied by advanced characterization techniques. It was found that iron in the oxide pellets is mainly in the form of brownmillerite, and calcium–iron–titanate phases, while upon reduction they are converted to wüstite and shulamitite intermediate phases and further to metallic iron. Moreover, it was found that the reduction at lower temperature of 1000 °C is faster than that at higher temperatures of 1100 °C and 1200 °C. The slower rate and extent of reduction at the higher temperatures is attributed to the porosity loss and reduction mechanism change to a diffusion-controlled process step. In addition, it was found that Al-containing phases in the raw materials are converted mainly to gehlenite in sintered pellets and further to the leachable mayenite phase. The alkaline leaching of selected reduced pellets by a sodium carbonate solution yielded up to 87% Al recovery into the solution, while the metallic iron was not affected.
1 April 2021 in ACS Sustainable Chemistry & Engineering
The application of natural gas instead of solid carbon to produce ferromanganese is a way forward in sustainable development. Mass and energy balances for an integrated duplex process to produce ferromanganese and direct reduced iron (DRI) by natural gas were studied. The process consists of natural gas injection into molten ferromanganese yielding carbon and hydrogen in which the dissolved carbon into the molten metal bath reduces MnO from a coexisting molten slag that is produced from the smelting of manganese ore. Hydrogen and CO gases reduce solid manganese oxides and iron oxides in the Mn ore to MnO and Fe in the ferromanganese reactor burden. A hot gas with a significant amount of CO and H2 leaves the reactor and is upgraded to a rich CO–H2 gas mixture via methane use in a gas reformer. The obtained highly reducing gas is then used to reduce iron ore in a direct reduction reactor for DRI production, while the DRI reactor process gas is partly looped into the gas reformer and the rest is used in an energy recovery unit for electric power generation for the ferromanganese reactor. It is shown that the presented duplex process is more sustainable than the current commercial ferromanganese production process and its application is accompanied by about 50% less electric energy consumption and about 40% less CO2 emission, excluding the source of electricity.