Materials and concepts for CO2 lean ironmaking by pyroelectrolysis

The main purpose of this PhD thesis was to provide convincing demonstration for a breakthrough concept of pyroelectrolysis at laboratory scale. One attempted to identify fundamental objections and/or the most critical constraints, to propose workable concepts for the overall process and for feasible electrodes, and to establish the main requirements on a clearer basis. The main effort was dedicated to studying suitable anode materials to be developed for large scale industrial units with molten silicate electrolyte. This concept relies on consumable anodes based on iron oxides, and a liquid Fe cathode, separated from the refractory materials by a freeze lining (solid) layer. In addition, one assessed an alternative concept of pyroelectrolysis with electron blocking membranes, and developed a prototype at small laboratory scale. The main composition of the molten electrolyte was based on a magnesium aluminosilicate composition, with minimum liquidus temperature, and with different additions of iron oxide. One studied the dynamics of devitrification of these melts, crystallization of iron oxides or other phases, and Fe2+/Fe3+ redox changes under laser zone melting, at different pulling rates. These studies were intended to provide guidelines for dissolution of raw materials (iron oxides) in the molten electrolyte, to assess compatibility with magnetite based consumable anodes, and to account for thermal gradients or insufficient thermal management in large scale cells. Several laboratory scale prototype cells were used to demonstrate the concept of pyroelectrolysis with electron blocking, and to identify the most critical issues and challenges. Operation with and without electron blocking provided useful information on transport properties of the molten electrolyte (i.e., ionic and electronic conductivities), their expected dependence on anodic and cathodic overpotentials, limitations in faradaic efficiency, and onset of side electrochemical reactions. The concept of consumable anodes was based on magnetite and derived spinel compositions, for their expected redox stability at high temperatures, even under oxidising conditions. Spinel compositions were designed for prospective gains in refractoriness and redox stability in wider ranges of conditions (T, pO2 and anodic overpotentials), without excessive penalty for electrical conductivity, thermomechanical stability or other requirements. Composition changes were also mainly based on components of the molten aluminosilicate melt, to avoid undue contamination and to minimize the dissolution rate of consumable anodes. Additional changes in composition were intended for prospective pyroelectrolysis of Fe alloys, with additions of different elements (Cr, Mn, Ni, Ti).

Contributo e caracterização de PM da ressuspensão rodoviária

Nos últimos anos, tem-se assistido a um crescimento no interesse do estudo da ressuspensão de pó de estrada, dado o reconhecimento da importância que esta fração representa para os níveis de partículas atmosféricas em ambiente urbano. Dada a prematuridade deste tema e, de forma a compreender e conhecer a sua contribuição e caracterização, realizou-se um estudo sobre a ressuspensão de pó de estrada urbano para as cidades do Porto e Braga. No âmbito do projeto AIRUSE e URBE, realizaram-se amostragens de PM10 no terreno com um dispositivo de amostragem móvel e em ambiente laboratorial com uma câmara de ressuspensão, sendo posteriormente analisado o seu conteúdo carbonoso por um sistema de análise termo-ótico de transmitância e, os elementos por ICP-MS e ICP-AES. Da campanha in situ resultaram cargas de PM10 compreendidas entre 0.190 e 49.5 mg.m-2 para a cidade do Porto e 0.577 mg.m-2 para o túnel rodoviário em Braga. As amostras caracterizam-se por serem dominadas pelos elementos Al, Fe, K, e Ca e conterem enriquecimentos de Sb, Fe, Cu, Sn e Zn, fruto da contaminação antropogénica da atividade rodoviária. No que respeita às amostragens em laboratório, utilizou-se uma câmara de ressuspensão e o dispositivo móvel aplicado na campanha anteriormente descrita para estudar e caracterizar a fração PM10 do pó de estrada urbano proveniente do Túnel Avenida da Liberdade (Braga). Os resultados obtidos para as duas metodologias foram de um modo geral similares, com o carbono total a representar cerca de 6% da massa total de PM10. Esta última é composta maioritariamente por Al, Fe, Ca e K, elementos característicos da crosta terrestre. Quanto ao fatores de enriquecimento calculados, denotou-se a presença de Sb, Zn, Cu e Sn, tendo-se associando ao desgaste dos travões e pneus.