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Intensifying CO2 photoreduction into value-added fuels using microscale illumination

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Multistage treatment for olive mill wastewater: Assessing legal compliance and operational costs
Publication . Vuppala, Srikanth; Paulista, Larissa Oliveira; Morais, Daniela F.S.; Pinho, Inês L.; Martins, Ramiro; Gomes, Ana I.; Moreira, Francisca C.; Vilar, Vítor J.P.
A treatment train for the remediation of a raw olive mill wastewater (OMW) was investigated, aiming to comply with the emission limit values (ELVs) for direct discharge into water bodies. The following stages were proposed: (i) pre-treatment (filtration and sedimentation), (ii) coagulation, (iii) biological oxidation, and (iv) advanced oxidation process (AOP). Under the best-operating conditions for coagulation (0.8 g L- 1 of Al2(SO4)3, pH = 4.5), high removal of total suspended solids (TSS) (97%), turbidity (98%), and phenols (57%) was achieved, along with a decrease in the inhibition of the biological activity. A subsequent biological oxidation stage provided a high removal of organic matter (chemical oxygen demand (COD) removal of 73%). For the third stage, three AOPs were applied and compared – photo-Fenton with UVA radiation (PF-UVA), anodic oxidation (AO), and ozonation (O3). After 3 h of treatment, the PF-UVA process (pH = 2.8, [H2O2] = 400–500 mg L- 1, [Total dissolved iron]0 = 100 mg L- 1) allowed to meet the ELV for COD, but the other parameters exceeded the threshold, while O3 process (inlet concentration = 100 mg O3 Ndm- 3, gas flow = 0.2 Ndm3 min- 1) allowed to comply with phenols, TSS, and sulfate limits. The AO process (current density up to 200 mA cm- 2) was the least efficient AOP for all studied parameters. The operational costs for the coagulation and biological oxidation stages were estimated at 1.20 € m- 3. Regarding the most effective AOPs, ozonation presented an estimated cost 2.3-fold higher than PF-UVA (11.9 € m- 3 vs. 5.2 € m- 3).
Solar-driven thermo-photocatalytic CO2 methanation over a structured RuO2:TiO2/SBA-15 nanocomposite at low temperature
Publication . Paulista, Larissa Oliveira; Ferreira, Alexandre; Castanheira, Bruna; Ðolić, Maja B.; Martins, Ramiro; Boaventura, Rui; Vilar, Vítor J.P.; Silva, Tânia F.C.V.
A new hybrid catalyst composed of mesostructured silica SBA-15 functionalized with TiO2 and further loaded with RuO2 was developed to efficiently promote thermo-photocatalytic CO2 hydrogenation into methane at low temperatures. The catalytic activity was assessed with respect to TiO2:RuO2 loading, catalyst dosage, illumination source (polychromatic sunlight and monochromatic LEDs) and power, [H2]:[CO2] molar ratio, temperature, and catalyst reusability. The best methanation yields were attained for the RuO2(6.4%):TiO2(16.9%)/SBA-15 nanocomposite at 150 ºC, under simulated sunlight (0.21 W) and stoichiometric [H2]:[CO2] molar ratio, reaching: a specific CH4 production rate of 13.6 mmol g-c1a t h-1; 99.8 % selectivity; 96.8 % CO2 conversion (110- min; 40 mL); and apparent photonic efficiency/quantum yield of 39.5 %/42.1 %. Considering only the active RuO2:TiO2 photocatalyst mass (23.3 %), the CH4 production rate increased to 58.6 mmol g-a1c tive_cat h-1. Besides, this highly-active photocatalyst featured excellent UV-Vis-IR light absorbance, high surface area, and stability for reuse when moist gas was removed between cycles.

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Funding agency

Fundação para a Ciência e a Tecnologia

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Funding Award Number

SFRH/BD/137639/2018

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