Browsing by Author "Fonseca, Isabel Maria"
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- Activated carbons from the co-pyrolysis of rice wastes for Cr(III) removalPublication . Dias, Diogo; Bernardo, Maria; Lapa, Nuno; Pinto, Filomena; Matos, Inês; Fonseca, Isabel MariaABSTRACT: Rice husk and polyethylene were mixed (50 % w/w each) and submitted to a pyrolysis assay. Four physical activations with CO2 were performed on the resulting co-pyrolysis char (PC). The activation at 800 °C, for 4h, generated the activated carbon (PAC3) with the best textural properties. PC, PAC3 and a commercial activated carbon (CAC) were characterized and submitted to Cr(III) removal assays. PC had a high percentage of volatile matter that was removed after the physical activation, resulting in more available pores in the final material (PAC). In the Cr(III) removal assays, two S/L ratios were tested: 5 and 10 g L-1. PC did not remove any Cr(III) from the solutions, but PAC presented similar results to CAC. At the S/L of 5 g L-1, Cr(III) removal was of 58.5 % for PAC and 62.5 % for CAC, both by adsorption mechanism; at the S/L of 10 g L-1, Cr(III) removal was almost complete due to precipitation caused by pH increase. The highest uptake capacities were of 7.92 mg g-1 for PAC and 8.71 mg g-1 for CAC, at the S/L of 5 g L-1. The results indicated that PAC3 may be a viable alternative to CAC on Cr(III) removal from aqueous media.
- Cattle fat valorisation through biofuel production by hydrogenation in supercritical carbon dioxidePublication . Morais, Ana Rita C.; Lopes, André; Costa, Paula; Fonseca, Isabel Maria; Nogueira, Isabel N.; Oliveira, Ana Cristina; Lukasik, Rafal M.The use of residues or wastes in biofuel production is a potential solution to the questioned increase of the food market price. The hydrogenation (more specifically hydrodeoxygenation) of residues or wastes rich in free fatty acids seems to be an interesting option for the valorisation of this type of feedstock. The major obstacle of this process is the high temperature and high H2 pressure process requirement. The way to reduce it is the use of a co-solvent e.g. supercritical fluids. At supercritical conditions, CO2 is completely miscible with H2 and at the same time is also a great solvent for non-polar liquids allowing enhanced efficiency of the hydrogenation leading to the ability to perform reactions at milder conditions. This work deals with the heterogeneous hydrogenation of cattle fat in the presence of CO2. Total reaction pressures up to 140 bar at 340 C and the residence time from 1 to 6 hours as well as the reuse of catalyst were examined. Depending on the chosen reaction conditions a diverse end products can be obtained. The CO2 presence influences positively the concentration of hydrocarbons minimising the presence of glycerides' content in the final product mixture. At elevated CO2 pressure, a high concentration of hydrocarbons simultaneously with a low presence of free fatty acids and glycerides' content in the mixture was obtained. A similar effect was observed for reaction carried out for 6 hours, when above 90 wt% of all hydrocarbons present in the mixture were the saturated ones. Additionally, the reuse of catalyst increases the saturated hydrocarbons' content to values similar to those obtained for reactions with prolonged residence time. In the CO2-assisted reactions, the diesel-like hydrocarbons were formed with at least two fold higher content than in reactions without CO2.
- Cr(III) dynamic removal in a fixed-bed column by using a co-gasification charPublication . Dias, Diogo; Bernardo, Maria; Pinto, Filomena; Fonseca, Isabel Maria; Lapa, NunoABSTRACT: A char (GC) obtained from the co-gasification of rice husk and polyethylene was used in a fixed-bed column with continuous flow for Cr(III) removal assays from synthetic and industrial wastewaters. For comparison purposes, a commercial activated carbon (CAC) was also used. The best experimental conditions in the continuous removal assays were the following ones: Cr(III) inflow concentration = 5 mg L-1, feed flow rate = 3 mL min(-1), mass of adsorbent in the column = 0.8 g, and inflow temperature = 50 degrees C. Under these conditions, the highest uptake capacities were 1.60 and 2.14 mg g(-1) in the synthetic solution, and 3.25 and 7.83 mg g(-1) in the industrial wastewater, for GC and CAC, respectively. These results are different from those obtained under batch conditions in which GC performed better than CAC. Cr(III) removal by both adsorbents occurred due to precipitation, but CAC presented a slightly higher amount of Cr(III) removed due to its highest porosity. The regeneration of GC and CAC was also studied, but both adsorbents showed no capacity to be used in more than one cycle. This study highlighted the importance of studying Cr(III) removal under continuous conditions, as the removal mechanisms may be completely different from the batch assays, affecting the adsorbents' performance.
- Cr(III) removal from synthetic and industrial wastewaters by using co-gasification chars of rice waste streamsPublication . Dias, Diogo; Lapa, Nuno; Bernardo, Maria; Ribeiro, W.; Matos, Inês; Fonseca, Isabel Maria; Pinto, FilomenaABSTRACT: Blends of rice waste streams were submitted to co-gasification assays. The resulting chars (G1C and G2C) were characterized and used in Cr(III) removal assays from a synthetic solution. A Commercial Activated Carbon (CAC) was used for comparison purposes. The chars were non-porous materials mainly composed by ashes (68.3-92.6% w/w). The influences of adsorbent loading (solid/liquid ratio - S/L) and initial pH in Cr(III) removal were tested. G2C at a S/L of 5 mg L-1 and an initial pH of 4.50 presented an uptake capacity significantly higher than CAC (7.29 and 2.59 mg g(-1), respectively). G2C was used in Cr(III) removal assays from an industrial wastewater with Cr(III) concentrations of 50, 100 and 200 mg L-1. Cr(III) removal by precipitation (uptake capacity ranging from 11.1 to 14.9mg g(-1)) was more effective in G2C, while adsorption (uptake capacity of 16.1 mg g(-1)) was the main removal mechanism in CAC.
- Highly efficient porous carbons for the removal of W(VI) oxyanion from wastewatersPublication . Dias, Diogo; Don, Davide; Jandosov, Jakpar; Bernardo, Maria; Pinto, Filomena; Fonseca, Isabel Maria; Sanches, André; Caetano, P. S.; Lyubchyk, Svitlana; Lapa, NunoABSTRACT: Pyrolysis chars derived from rice wastes were chemically activated and used in W(VI) oxyanion adsorption assays in synthetic and mining wastewaters. For comparison purposes, a commercial activated carbon (CAC) was also used. Different experimental conditions were tested in the adsorption assays: solid/liquid ratio (S/L), initial pH, contact time, and initial W concentration. The porous carbon P2C+KOH presented the overall best performance in both media, due to its high surface area (2610 m2 g-1), mesopore volume (1.14 cm3 g-1), and neutral pHpzc (6.92). In the synthetic wastewater, the highest uptake capacity of P2C+KOH (854 mg g-1) was found in the assays with an S/L 0.1 g L-1, an initial pH 2, and an initial W concentration of 150 mg L-1, for 24 h. This value was almost 8 times higher than the one obtained for CAC (113 mg g-1). In the mining wastewater, P2C+KOH showed an even higher uptake capacity (1561 mg g-1) in the assay with the same experimental conditions, which was almost 3 times higher than for CAC (561 mg g-1). These results suggest that P2C+KOH seems to be an efficient alternative to CAC in the W(VI) adsorption from liquid effluents.
- Recovery of Nd3+ and Dy3+ from E-Waste Using Adsorbents from Spent Tyre Rubbers: Batch and Column Dynamic AssaysPublication . Nogueira, Miguel; Matos, Inês; Bernardo, Maria; Pinto, Filomena; Fonseca, Isabel Maria; Lapa, NunoABSTRACT: This paper investigates the use of spent tyre rubber as a precursor for synthesising adsorbents to recover rare earth elements. Through pyrolysis and CO2 activation, tyre rubber is converted into porous carbonaceous materials with surface properties suited for rare earth element adsorption. The study also examines the efficiency of leaching rare earth elements from NdFeB magnets using optimised acid leaching methods, providing insights into recovery processes. The adsorption capacity of the materials was assessed through batch adsorption assays targeting neodymium (Nd3+) and dysprosium (Dy3+) ions. Results highlight the superior performance of activated carbon derived from tyre rubber following CO2 activation, with the best-performing adsorbent achieving maximum uptake capacities of 24.7 mg.g(-1) for Nd3+ and 34.4 mg.g(-1) for Dy3+. Column studies revealed efficient adsorption of Nd3+ and Dy3+ from synthetic and real magnet leachates with a maximum uptake capacity of 1.36 mg.g(-1) for Nd3+ in real leachates and breakthrough times of 25 min. Bi-component assays showed no adverse effects when both ions were present, supporting their potential for simultaneous recovery. Furthermore, the adsorbents effectively recovered rare earth elements from e-waste magnet leachates, demonstrating practical applicability. This research underscores the potential of tyre rubber-derived adsorbents to enhance sustainability in critical raw material supply chains. By repurposing waste tyre rubber, these materials offer a sustainable solution for rare earth recovery, addressing resource scarcity while aligning with circular economy principles by diverting waste from landfills and creating value-added products.
- Sorption of lead (Pb2+) from aqueous solutions using chars obtained in the pyrolysis of forestry pine, rubber tires and plasticsPublication . Bernardo, Maria; Mendes, S.; Lapa, Nuno; Gonçalves, Maria Margarida; Mendes, Benilde; Pinto, Filomena; Fonseca, Isabel MariaCarbonaceous solid products resulting from thermochemical processes (pyrolysis, gasification), commonly known as chars, are emerging as low-cost sorbents of metallic contaminants, being their effectiveness already demonstrated in several studies (Inyang et al., 2012; Fuente-Cuesta et al., 2012; Ko³odyñska et al., 2012; Quek and Balasubramanian, 2009; Devecia and Kar, 2013). Given the fact that the commercial viability of pyrolysis and gasification plants for the treatment and valorisation of waste streams are increasingly being demonstrated, it is expected that large amounts of solid chars will be available in a near future, as by-products or as main products (pyrolysis-carbonization). Chars may possess several characteristics which turn them effective as heavy metals sorbents: aromatic carbon matrix with relatively porous structures, the presence of functional groups or inorganic inclusions in the surface providing active sites to interact with metallic species (Inyang et al., 2012; Fuente-Cuesta et al., 2012; Ko³odyñska et al., 2012; Quek and Balasubramanian, 2009; Devecia and Kar, 2013; Lu et al., 2012). Lead (Pb2+) is considered as a priority substance in the field of European water policy (EU, 2000; EU, 2008) which means that measures shall be taken by the Member States to eliminate or reduce the water pollution caused by this pollutant in order to fulfill the emission/discharge limits legislated for this compound.
- Valorisation of spent tire rubber as carbon adsorbents for Pb(II) and W(VI) in the framework of a Circular EconomyPublication . Bernardo, Maria; Lapa, Nuno; Pinto, Filomena; Nogueira, Miguel; Matos, Inês; Ventura, Márcia; Ferraria, Ana Maria; Rego, Ana Maria Botelho do; Fonseca, Isabel MariaABSTRACT: Spent tire rubber-derived chars and their corresponding H3PO4 and CO2-activated chars were used as adsorbents in the recovery of Pb(II) ion and (W(VI)) oxyanion from synthetic solutions. The developed chars (both raw and activated) were thoroughly characterized to have insight about their textural and surface chemistry properties. H3PO4-activated chars presented lower surface areas than the raw chars and an acidic surface chemistry which affected the performance of these samples as they showed the lowest removals of the metallic ions. On the other hand, CO2-activated chars presented increased surface areas and increased mineral content compared to the raw chars, having presented higher uptake capacities for both Pb(II) (103-116 mg/g) and W(VI) (27-31 mg/g) ions. Cation exchange with Ca, Mg and Zn ions was appointed as a mechanism for Pb removal, as well as surface precipitation in the form of hydrocerussite (Pb-3(CO3)(2)(OH)(2)). W(VI) adsorption might have been ruled by strong electrostatic attractions between the negatively charged tungstate species and the highly positively charged carbons' surface.The results shown in this work allow concluding that the valorisation of spent tire rubber through pyrolysis and the subsequent activation of the obtained chars is an alternative and a feasible option to generate adsorbent materials with a high uptake capacity of critical metallic elements.