• Energy Research

In the present work, the enhancement of biogas and methane yields through anaerobic co-digestion of the pre-hydrolised Organic Fraction of Municipal Solid Wastes (hOFMSW) and Maize Cob Wastes (MCW) in a lab-scale thermophilic anaerobic reactor was tested. In order to increase its biodegradability, MCW were submitted to an initial pre-treatment screening phase as follows: (i) microwave (MW) irradiation catalysed by NaOH, (ii) MW catalysed by glycerol in water and alkaline water solutions, (iii) MW catalysed by H2O2 with pH of 9.8 and (iv) chemical pre-treatment at room temperature catalysed by H2O2 with 4 h reaction time. The pre-treatments cataysed by H2O2 were performed with 2% MCW (wMCW/v alkaline water) at ratios of 0.125, 0.25, 0.5 and 1.0 (wH2O2/wMCW). The pre-treatment that presented the most favourable balance between sugars, lignin, cellulose and hemicellulose solubilisations, as well as low production of phenolic compound and furfural (inhibitors), was the chemical pre-treatment catalysed by H2O2, at room temperature, with a ratio of 0.5 wH2O2/wMCW (Pre1). This Pre1 was then optimised testing reaction times of 1, 2 and 3 days at a different pH (11.5) and MCW percentage (10% w/v). The optimised pre-treatment that presented the best results, considering the same criteria defined above, was the one carried out during 3 days, at pH 9.8 and 10% MCW w/v (Pre2). The anaerobic reactor was initially fed with the hOFMSW obtained from the hydrolysis tank of an industrial AD plant. The hOFMSW was than co-digested with MCW submitted to the pre-treatment Pre1. In another assay, hOFMSW was co-digested with MCW submitted pre-treatment Pre 2. The co-digestion of hOFMSW + Pre1 increased the biogas yield by 38.9% and methane yield by 29.7%, when compared to the results obtained with hOFMSW alone. The co-digestion of hOFMSW + Pre2 increased biogas yield by 46.0% and CH4 yield by 36.3%. In both cases, the methane content obtained in the biogas streams was above 66% v/v. These results show that pre-treatment with H2O2, at room temperature, is a promising low cost way to valorize MCW through co-digestion with hOFMSW.

Life cycle assessment (LCA) is a powerful tool to quantify the environmental burdens of different analytical techniques. This work assesses the environmental impacts associated with the use of a simple electrochemical carbon paper sensor (CPS) for ketoprofen detection in fish by LCA in comparison with traditional liquid high-performance chromatography (HPLC) with fluorescent detection. The results indicate significant advantages of CPS compared to HPLC in 16 of the 18 analyzed categories of impact (ReCiPe2016(H) method), with average CPS values 26% lower than for HPLC. This is due, in the categories of impact with higher environmental relevance, to the higher electric energy consumption during the “Analysis” step and, secondarily, to the use of acetonitrile as a mobile phase. On an annual basis, ketoprofen detection by CPS saves 333 kg 1.4 dichlorobenzene equivalents (1.4 DCB eq) of non-carcinogenic and 6.9 kg 1.4 DCB eq of carcinogenic human toxicities, 43.6 kg oil eq of fossil resources, and 91.4 kg CO2 eq of greenhouse gas emissions compared to HPLC. The high capital investment, maintenance costs, and reagents quantities required for HPLC mitigate the economic competitiveness of this traditional technique compared to the rapid and less complex portable CPS device under the studied conditions.

Several pesticides and pharmaceuticals (PP) have been detected in the effluent of a full-scale Portuguese Wastewater Treatment Plant (WWTP). Their presence contributed to the environmental burdens associated with the existing treatment of the Municipal Wastewater (MWW) in the impact categories of Human Carcinogenicity, Non-Carcinogenicity, and Freshwater toxicities on average by 85%, 60%, and 90%, respectively (ReciPe2016 and USEtox methods). The environmental and economic assessment of the installation of an Anodic Oxidation (AO) unit for PPs’ removal was performed through Life Cycle and Economic Analysis, considering two types of anodes, the Boron-Doped Diamond (BDD) and the Mixed Metal Oxides (MMO). The operation of the AO unit increased the environmental burdens of the system by 95% on average (USEtox), but these impacts can be partially compensated by the avoided the production of non-renewable energy in the Portuguese electricity mix by biogas cogeneration at the WWTP. If the construction of the AO unit and the manufacturing of the electrodes are considered, the Human and Freshwater Toxicities are often higher than the environmental benefits derived from the PPs’ removal. On the economic side, the MMO configuration is clearly more advantageous, whereas BDD is environmentally more favorable. The issue of the presence of PP in MWW effluents has to be addressed as an integrated solution both improving upstream PP’s management and adopting PP’s removal technologies strongly supported by renewable energies. Further insights are needed for the assessment of fate and of the environmental effects of PP in the sludge.

Maize Cob Waste (MCW) is available worldwide in high amounts, as maize is the most produced cereal in the world. MCW is generally left in the crop fields, but due to its low biodegradability it has a negligible impact in soil fertility. Moreover, MCW can be used as substrate to balance the C/N ratio during the Anaerobic co-Digestion (AcoD) with other biodegradable substrates, and is an excellent precursor for the production of Activated Carbons (ACs). In this context, a biorefinery is theoretically discussed in the present review, based on the idea that MCW, after proper pre-treatment is valorised as precursor of ACs and as co-substrate in AcoD for biomethane generation. This paper provides an overview on different scientific and technological aspects that can be involved in the development of the proposed biorefinery; the major topics considered in this work are the following ones: (i) the most suitable pre-treatments of MCW prior to AcoD; (ii) AcoD process with regard to the critical parameters resulting from MCW pre-treatments; (iii) production of ACs using MCW as precursor, with the aim to use these ACs in biogas conditioning (H2S removal) and upgrading (biomethane production), and (iv) an overview on biogas upgrading technologies.

A Life Cycle Analysis (LCA) based on ReCiPe 2016 model of a biorefinery case-study was performed. On the basis of an existing Portuguese Anaerobic Digestion plant, the proposed biorefinery hypothesized the use of (i) Maize Cob Waste (MCW) as co-substrate for Anaerobic co-Digestion (AcoD) with Organic Fraction Municipal Solid Waste (OFMSW), (ii) the use of MCW derived activated carbons (ACs) in a H2S removal unit, and (iii) the biogas upgrading to biomethane in a Pressure Swing Adsorption unit. The main aim was to compare the environmental benefits obtained from distinct uses of biogas, specifically the cogeneration of electricity/heat and biomethane production.Three biogas production configurations were considered: (i) AD of standalone hydrolysed OFMSW (hOFMSW); (ii) AcoD of hOFMSW and MCW pre-treated with H2O2 (hOFMSW+PreMCW); and (iii) AcoD of hOFMSW with non-pre-treated MCW (hOFMSW+MCW). The increase of biogas and methane yields obtained with AcoD of hOFMSW+MCW provided an overall better environmental performance than other configurations.The biogas upgrading to biomethane from AcoD of hOFMSW+MCW generated higher environmental impacts than cogeneration, due to the AC production and upgrading processes. If an optimised H2S adsorption capacity is considered, the Fossil Resource Scarcity, Mineral Resource Scarcity, and Global Warming human health impact categories decreased by 20%, 15%, and 17%, respectively, when compared to the base-case upgrading scenario. Further decreases of up to 52%, 23%, and 28% for those impact categories, respectively, are observed when the natural gas used in the OFMSW collection and transportation fleet is substituted by biomethane produced in the biorefinery.