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- Chemical and bioassay fractionation of chars obtained in the co-pyrolysis of different wastesPublication . Bernardo, Maria; Lapa, Nuno; Gonçalves, Maria Margarida; Mendes, Benilde; Pinto, FilomenaThe present work is devoted to the study chars obtained in the co-pyrolisis of plastics, biomass and tyres wastes. The composition of these chars is not yet well studied and only recent an attempt was made by the aithors to provide some information about the composition and risk assessment of these materials. The objectives of this work were to perform solvent extractions, using differents, in chars obtained in the co-pyrolysis process to evaluate the extraction efficiency by characterising the different solvent extracts obtained as well as the extracted chars, to perform a chemical ans bioassay franctionation in the most toxic crude extraction in order to study the chemical composition of the fractions as well as their individual contribution to the global toxicity of the crude extarct. The results will allow to conclude which solvent should be used in the decontamination of the pyrolysis chars.
- Evaluation of the environmental hazard of char residues produced in the co-pyrolysis of different wastes :chemical and ecotoxicological characterizationPublication . Bernardo, Maria; Lapa, Nuno; Gonçalves, Maria Margarida; Barbosa, Rui; Mendes, Benilde; Pinto, Filomena; Gulyurtlu, IbrahimChar residues produced in co-pyrolysis of different wastes were characterized through chemical and toxicity tests. A fraction of the solid chars was treated by extraction with dichloromethane. Different volatilit fractions present in the extracted and non extrated char were evaluated. A selected group of heavy metals was determined in both chars. Chars were subjected to the leaching test ISO/TS 21268-2 and resulting eluates were further characterized by determining a group of inorganic parameters and concentrations of several organic contaminants. An ecotoxicological characterization was performed by using the bio-indicator Vibrio fischeri. The chemical and ecotoxicological characterization led to a classification on the chars as ecotoxic
- Evaluation of the toxicity of char residues produced in the co-pyrolysis of different wastesPublication . Bernardo, Maria; Lapa, Nuno; Gonçalves, Maria Margarida; Barbosa, Rui; Mendes, Benilde; Pinto, FilomenaThe high amounts of solid waste produced in industrial installations and in urban centers is a complex problem of today's society. The traditional strategies for solid waste transformation and disposal include and filling or incineration. Other approaches are being exploited namely waste selective collection and recycling on the energetic valorization of solid wastes through pyrolysis. In the pyrolytic process, the wastes are converted into a gaseous and liquid phase that can be used in energy production or as feedstock in chemistry industries. A solid residue (char) is also produced in a proportion that depends on the pyrolysis conditions. Even when the operating condiions are optimized in order to minimize the solid fraction, a resonable amount of chars are obtained. Those chars are mainly composed of a carbon-rich matrix that contains the mineral matter initially present in the wastes as well as components of the liquid fraction. Therefore, these solid residues have a toxicity potential due to the presence of heavy metals or organic compounds that must be assessed in order to define their safe reutilization or disposal. In the present study, the chars produced in the co-pyrolysis of plastics, pine biomass and tyres were characterized through chemical and ecotoxicological tests. A fraction of the solid chars was treated by extraction with dichloromethane. Different volatibility groups of compounds present in the extracted and non extracted char were evaluated. A selected group of heavy metals was determined in both chars. Chars were subjected to the leaching test ISO/TS 21268-2 and the resulting eluates were further characterized by determining a group of inorganic and organic parameters. An ecotoxicological characterization was performed by using he bio-indicator Vibrio fischeri. The chemical and ecotoxicological results were compared and analysed according to the council Decision 2003/33/CE and the Criteria on the Evaluation Methods of Waste Ecotoxicity (CEMWE). The results of the chemical characterization indicate that the extraction of the char residues with an appropriate organic solvent allows the sufficient elimination of the volatile organic contaminants thus decreasing the potential toxicity of these chars. The semi-volatile and non-volatile fractions were not, apparently, affected by this pre-treatment. Regarding the release of heavy metals from extracted and non-extracted chars during the leaching tests, a strong contamination with Zn was found in both eluates, which contribute to a classification of the corresponding chars as hazardous and ecotoxic materials. Also the results of the ecotoxicological characterization of the eluates led to a classification of these chars as ecotoxic materials.
- 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.
- Leaching behaviour and ecotoxicity evaluation of chars from the pyrolysis of forestry biomass and polymeric materialsPublication . Bernardo, Maria; Mendes, S.; Lapa, Nuno; Gonçalves, Maria Margarida; Mendes, Benilde; Pinto, Filomena; Lopes, HelenaThe main objective of this study was to assess the environmental risk of chars derived from the pyrolysis of mixtures of pine, plastics, and scrap tires, by studying their leaching potential and ecotoxicity. Relationships between chemical composition and ecotoxicity were established to identify contaminants responsible for toxicity. Since metallic contaminants were the focus of the present study, an EDTA washing step was applied to the chars to selectively remove metals that can be responsible for the observed toxicity. The results indicated that the introduction of biomass to the pyrolysis feedstock enhanced the acidity of chars and promote the mobilisation of inorganic compounds. Chars resulting from the pyrolysis of blends of pine and plastics did not produce ecotoxic eluates. A relationship between zinc concentrations in eluates and their ecotoxicity was found for chars obtained from mixtures with tires. A significant reduction in ecotoxicity was found when the chars were treated with EDTA, which was due to a significant reduction in zinc in chars after EDTA washing.
- 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.
- 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.
- 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.
- 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.
- 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.