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- Corrosão de aços inoxidáveis austeníticos em sais fundidos ternários de cálcioPublication . Cunha Diamantino, Teresa; Gomes, A.; Paiva Luís, Teresa; Figueira, Isabel; Pedrosa, Fátima; Nogueira, Carlos; Guerreiro, L.; Collares-Pereira, M.RESUMO: O armazenamento de energia térmica (TES) é um fator chave para melhorar a eficiência e a despachabilidade dos diferentes sistemas energéticos, devido a um melhor ajustamento entre a procura e a oferta de energia, e ao permitir o desenvolvimento e a implementação de energias renováveis. Um exemplo claro é o TES em instalações de concentração de energia solar (CSP), onde o excesso de energia solar durante o período de luz solar é armazenado para ser utilizado durante os períodos em que a energia solar é necessária, mas não está disponível. Os sais fundidos têm sido amplamente utilizados como fluidos de transferência de calor (HTF) e para TES em instalações CSP. Uma das características fundamentais dos sais fundidos no que diz respeito à sua utilização como HTF e TES é a sua compatibilidade com os materiais de construção. Por esta razão, este trabalho apresenta a resistência à corrosão de dois aços inoxidáveis austeníticos AISI 316L e AISI 321H em contacto com sal ternário fundido com cálcio. Ambos os aços inoxidáveis demonstraram ter velocidades de corrosão aceitáveis para as centrais CSP. Entre os aços austeníticos estudados, o AISI 316L apresenta a menor velocidade de corrosão.
- End-of-life Zn–MnO2 batteries: electrode materials characterizationPublication . Cabral, Marta; Pedrosa, Fátima; Margarido, F.; Nogueira, CarlosPhysical and chemical characterization of several sizes and shapes of alkaline and saline spent Zn–MnO2 batteries was carried out, aiming at contributing for a better definition of the applicable recycling processes. The characterization essays included the mass balance of the components, cathode and anode elemental analysis, the identification of zinc and manganese bearing phases and the morphology analysis of the electrode particles. The electrode materials correspond to 64–79% of the total weigh of the batteries, with the cathodes having clearly the highest contribution (usually more than 50%). The steel components, mainly from the cases, are also important (17–30%). Elemental analysis showed that the electrodes are highly concentrated in zinc (from 48–87% in anodes) and manganese (from 35–50% in cathodes). X-Ray powder diffraction allowed for identifying several phases in the electrodes, namely zinc oxide, in the anodes of all the types of saline and alkaline batteries tested, while zinc hydroxide chloride and ammine zinc chloride only appear in some types of saline batteries. The manganese found in the cathode materials is present as two main phases, MnO·Mn2O3 and ZnO·Mn2O3, the latter corroborating that zinc migration from anode to cathode occurs during the batteries lifespan. A unreacted MnO2 phase was also found presenting a low crystalline level. Leaching trials with diluted HCl solutions of alkaline and saline battery samples showed that all zinc species are reactive attaining easily over than 90% leaching yields, and about 30% of manganese, present as Mn(ii/iii) forms. The MnO2 phase is less reactive and requires higher temperatures to achieve a more efficient solubilization.
- Dynamic corrosion testing of metals in solar salt for concentrated solar powerPublication . Sutter, Florian; Oskay, Ceyhun; Galetz, Mathias Christian; Cunha Diamantino, Teresa; Pedrosa, Fátima; Figueira, Isabel; Glumm, Stefan; Bonk, Alexander; Aguero, Alina; Rodríguez, Sergio; Reche-Navarro, Tomas Jesus; Caron, SimonABSTRACT: Potassium nitrate and sodium nitrate in mixing proportion of KNO3-NaNO3 40-60 wt% (also called solar salt) has been successfully used for over a decade as heat storage medium for concentrated solar power parabolic-trough collector plants at temperatures up to 400 degrees C. At temperatures of 560 degrees C, reached in state-of-the-art solar tower systems, corrosion of metallic components in contact with solar salt can become an issue and has caused leaks and plant shut-downs in recently built tower projects. While the corrosion rates of several materials have been determined for different temperatures in static molten salt immersion experiments, there is a lack of corrosion data for dynamic in-service conditions. In this work, a dynamic corrosion test has been conducted on 19 different material types including protective coatings, mimicking flow-rate, temperature gradient and draining of inservice operation of a receiver in a concentrated solar power tower. The measured corrosion rates are presented and compared to static corrosion tests reported in literature.
- Recycling of zinc bearing residues: leaching behavior of spent batteries and eaf dusts in several aqueous mediaPublication . Pedrosa, Fátima; Cabral, Marta; Nogueira, Carlos
- Hot Corrosion Behavior of Slurry Sprayed Aluminide Coatings in a Simulated Dynamic Molten Carbonate Environment [Comunicação oral]Publication . Audigié, Pauline; Rodríguez Catela, Sergio; Agüero, Alina; Pedrosa, Fátima; Paiva Luís, Teresa; Cunha Diamantino, TeresaABSTRACT: One of the key challenges associated with the use of molten salts in Concentrated Solar Power (CSP) plants is to reduce or even suppress corrosion phenomena occurring at elevated temperatures. Molten nitrate mixtures are currently seen as the most viable storage medium for Thermal Energy Storage. But the upper temperature limit of the currently used “Solar Salt” is restricted by salt decomposition at ~580ºC. Prieto et al. estimated that increasing the temperature to 650ºC could increase the solar-to-electric conversion up to 18.5%, so alternative salts operating at higher temperature are required. Molten carbonates which are less corrosive and allow an operation up to 800ºC are an appealing breakthrough for future CSP plants.
- Separation of non-ferrous frations of shredded end-of-life vehicles for valorising its alloysPublication . Margarido, F.; Santos, R. Novais; Durão, F.; Guimarães, C.; Nogueira, Carlos; Oliveira, Paula; Pedrosa, Fátima; Gonçalves, Ana MariaWorldwide the end-of-life vehicles (ELV) generate millions of tons of waste, requiring an adequate and efficient management. The non-ferrous fraction contains essentially aluminium, magnesium and copper alloys, being valorised by metallurgical processors to obtain new metals and alloys. However most of the recovered metals are downcycled, as is the case of aluminium where the recycled products are essentially used to produce less purity casting alloys. New or improved separation technologies are therefore necessary in order to allow an accurate separation of alloys or alloy groups, increasing the value of the non-ferrous streams. In this paper, the composition of the non-ferrous fractions of ELV shredders are assessed with particular relevance for the aluminium and magnesium alloys. Essentially, the main cast and wrought alloys are characterized and their markets and applications are discussed. Based on waste composition, several physical separation and sorting technologies can be applied to improve the products quality, which are here depicted and discussed. Physical processing includes operations such as eddy current and heavy media separations. For sorting alloys contained in the non-ferrous stream, other sensor-based technologies are being developed, such as electromagnetic sensing and novel laser induced breakdown spectroscopy systems, constituting an important contribution for boosting the non-ferrous metals recycling rates.
- Molten nitrate salts containing lithium as thermal energy storage media : a short reviewPublication . Pedrosa, Fátima; Marcelo, Teresa; Nogueira, Carlos; Gomes, A.; Cunha Diamantino, TeresaABSTRACT: Energy storage plays a crucial role in the development and progress of renewable energy sources. In the case of thermal energy, storage has been a step ahead since storage solutions already exist, unlike other conversion energy technologies. In this sense, the utilization of molten salts, mainly composed of mixtures of alkali/alkaline earth metals, in nitrate forms (sometimes also with nitrite), have been proposed and successfully applied. Molten salts have recognized advantages over other solutions namely in what concerns simultaneous use as heat transfer fluids and as storage media. Commercial utilization of molten salts has been tested essentially with the Na/K salt mixtures. Introduction of lithium nitrate in these formulation has been proposed, since can allow decreasing the melting point of the mixtures, thus providing safety concerning the risks of freezing in the tubes or tanks of the storage plant. This paper provides a short review on the utilization of lithium in molten salt mixtures used for thermal energy storage. Physical, chemical and thermal properties, as well as stability and decomposition issues are evaluated. Corrosion of stainless steels in contact with the salts is another crucial question that is also addressed.
- Methodologies for assessing corrosion under dynamic conditions with molten salts in CSP/CST applications [Resumo]Publication . Cunha Diamantino, Teresa; Pedrosa, Fátima; Paiva Luís, Teresa; Figueira Vasques, Isabel; Gil, Mafalda; Navas, M.; Veca, E.ABSTRACT: Renewable energy implementation represents a key point in reversing global warming and climate change. In recent years, there has been an investment in Concentrated Solar Power (CSP) with Energy Storage (TES). Solar Salt is the most energy storage fluid optimized with a melting point of 223 °C and thermally stable up to about 550 °C. One of the most relevant problems in the use of fluids as thermal energy storage is their compatibility with construction materials (pipes, valves and tanks). This fact, combined with high temperatures (300-550 °C) makes the materials more susceptible to corrosion. Static immersion experiments are suited to screen and compare different candidate materials for molten salt applications (Fernández et al., 2019; Gomes et al. 2019), but corrosion rates derived from these experiments might differ significantly from the rates experienced in a real operating environment of a solar plant (Florian et al. 2021). There are currently no specific procedures for evaluating corrosion in molten salts under dynamic conditions, so it is important to develop more practical application conditions to validate methodologies and facilities. The main purpose of this work is to identify the suitable procedures to make a reproducible experimental dynamic corrosion test using an experimental set-up that can vary the velocity of molten salts over a wide range.
- Metals recovery from spent Zn-MnO2 batteries by HydrometallurgyPublication . Nogueira, Carlos; Guerra, R. N. G.; Pedrosa, Fátima; Margarido, F.A hydrometallurgical process for recycling spent Zn-MnO2 batteries was developed, involving leaching with sulfuric acid, purification by precipitation and metals separation for further recovery. Leaching of zinc oxide was easily attained while for manganese oxide was rather difficult depending on temperature and acid concentration. At 90ºC and with the liquid/solid ratio of 20 L/kg, more than 95% of zinc is recovered in 30 minutes with 0.5M H2SO4. To attain similar recovery for manganese, higher levels of acid concentration and time are needed (e.g 0.7 M and 2 hours). After leaching a purification step is necessary to remove iron co-dissolved through Fe(III) precipitation. Separation of zinc from manganese by solvent extraction with 1M DEHPA follows in the process route. The countercurrent multistage separation diagram developed allows the production of a zinc electrolyte with 120 g/L Zn and 0.005 g/L Mn, and a raffinate with 16 g/L Mn and 0.013 g/L Zn.
- Estudio de la resistencia frente a la corrosión por nitratos fundidos de recubrimientos basados en aluminuros en condiciónes dinamicasPublication . Rodríguez, Sergio; Audigié, Pauline; Agüero, A.; Pedrosa, Fátima; Paiva Luís, Teresa; Cunha Diamantino, TeresaRESUMEN: Recubrimientos de slurry de aluminio depositados sobre P91, un acero ferrítico-martensítico con un contenido de 9 % en peso de cromo, fueron estudiados y comparados con el material sin recubrir tras ser expuestos por inmersión en la Sal Solar (60 wt.% NaNO3 – 40 wt.% KNO3) a 580 ºC hasta 1000 h bajo condiciones dinámicas. Dos recubrimientos de aluminuros de diferente microestructura resultantes de la realización de dos tratamientos térmicos distintos después de la aplicación del slurry, fueron ensayados y se compararon los resultados con los obtenidos anteriormente en condiciones estáticas. En ambos casos, el P91 no recubierto mostró un gran descascarillado de los óxidos formados y fue necesario remover los productos de corrosión para realizar una correcta estimación de pérdida de peso. El óxido mostró una estructura de multicapa de Fe2O3, Fe3O4 y NaFeO2. Las muestras recubiertas mejoraron significativamente el comportamiento del material no recubierto, exhibiendo una variación de peso mucho menor. La composición y la microestructura de cada recubrimiento se mantuvieron después de 1000 h de ensayo en ambas condiciones de ensayo.
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