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- 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.
- Opportunities and Constraints of the Adsorption of Rare Earth Elements onto Pyrolytic Carbon-Based Materials: A Mini-ReviewPublication . Nogueira, Miguel; Bernardo, Maria; Ventura, Márcia; Matos, Inês; Pinto, Filomena; Lapa, NunoABSTRACT: Rare earth elements (REEs), comprising seventeen metallic elements, including lanthanides, scandium, and yttrium, are indispensable for modern technological industries due to their unique properties. However, their supply is critically risky for the European Union, with 95% of global production concentrated in China, Brazil, Vietnam, Russia, India, and Australia. This mini-review examines the adsorption of REEs onto pyrolytic carbon-based materials as a sustainable recovery method from secondary raw materials. The review covers different types of carbon-based adsorbents used in several research works, such as activated carbon, chars, and biochar, and discusses their adsorption mechanisms and influencing factors. Comparative analyses of adsorption capacities highlight the significance of surface area and functionalization in enhancing adsorption efficiency. Despite promising results, the variability in adsorption performance due to experimental conditions and the scarcity of real-world application studies are noticed. This review underscores the need for further research using real e-waste leachates to validate the practical applicability of pyrolytic carbon-based adsorbents for REEs' recovery, aiming for an economically and environmentally sustainable solution.
- 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.
- 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.