Produzione biologica di idrogeno da miscele di residui

2008-11-25Aula Magna Facoltà di Ingegneria, CagliariLo stato dell’arte della ricerca scientifica nel settore della produzione di energia da biomass

Biohydrogen production from food waste: Influence of the inoculum-to-substrate ratio

In this study, the influence of the inoculum-to-substrate ratio (ISR) on dark fermentative hydrogen production from food waste (FW) was evaluated. ISR values ranging from 0.05 to 0.25 g VSinoculum/g VSsubstrate were investigated by performing batch tests at T = 39 °C and pH = 6.5, the latter being the optimal value identified based on a previous study. The ISR was found to affect the fermentation process, clearly showing that an adequate ISR is essential in order to optimise the process kinetics and the H2 yield. An ISR of 0.14 proved to optimum, leading to a maximum H2 yield of 88.8 L H2/kg VSFW and a maximum production rate of 10.8 L H2/kg VSFW∙h. The analysis of the fermentation products indicated that the observed highest H2 production mostly derived from the typical acetate/butyrate-type fermentation

Trends and perspectives in the use of organic acids for critical metal recycling from hard-metal scraps

Hard-metal sector, strategic for the industrial economies, is suffering from the reduced availability and price volatility of its main feedstock: critical W and Co. In 2021, a 73.5 kt W and 9.2 kt Co demand for hard-metal production (65% and 5.3% of global demand, respectively), was recorded. Hard-metal scrap recycling is hence desirable for both environmental and economic reasons. A significant recovery of W and Co from manufacturing by-products and scraps is already good practice in the hard-metal industry (42% for W and 22% for Co). However, there is still a lot to do to meet the technical-economic-environmental sustainability in materials and energy enhancement for pursuing a green economy model. Indeed, Chemical Modification and Direct Recycling, which are the most widely employed industrial approaches, typically involve energy and/or harsh chemicals-intensive treatments which require expensive equipment and skilled workers. In the last decade, research efforts have been spent on implementing alternative materials reclamation processes from hard-metal scraps based on the use of bio-based organic acids with the view to increase the rate and quality of the recycled materials exploiting their peculiar metal complexing action as well as to preserve natural resources and prevent the disposal of potentially toxic/polluting substances. Despite the preliminary stage of the research, organic acids were demonstrated to be powerful but gentle agents for the selective leaching of cobalt from WC-Co-based materials as well as promising agents for WO3 dissolution. Indeed, thanks to their acid and complexing properties, they can stabilize metals in their oxidized form giving soluble products and preventing passivation phenomena. Furthermore, organic acids can be obtained by renewable biomass transformation, limiting the request for high-impact industrial chemicals. Hence they points out key features making them promising for the design of eco-friendly recovery processes. In this context, the different industrial approaches to the recovery and recycling of Hard-metal wastes, with specific reference to the role of bio-derived organic acids in hydro- and solvo-metallurgical processes, will be critically reviewed with the view of opening a discussion on the perspectives of their use in designing circular economy models in HM manufacturing as economically, technically and environmentally sustainable as possible

Disposable Mater-Bi® bioplastic tableware: Characterization and assessment of anaerobic biodegradability

In this study commercial starch-based (Mater-Bi®) disposable bioplastic tableware items, which are among the most widely used commercial products available on the market, were selected for lab-scale anaerobic degradability tests. Since the knowledge of the biodegradation profile of bioplastic products is still incomplete, the study was aimed at investigating the maximum biodegradation potential of the materials under ideal anaerobic conditions, as well as the biodegradability degree as a function of treatment time. The experiments were carried out under mesophilic and thermophilic conditions at different food to microorganism ratios and test material sizes, and the specific biogas production and associated kinetics were evaluated. Biogas production was observed only under thermophilic conditions, with conversion yields in the range 602–898 mL/gTOC for the tested cups and 1207 ± 52.8 mL/gTOC for the knives. The degrees of biodegradation and disintegration were found to be strongly dependent on the product composition. Physical, chemical and morphological analyses were used to characterize the tested materials before and after the degradation and potential correlations among process parameters and bioplastic characteristics were derived

A Case Study of Implementation of Circular Economy Principles to Waste Management: Integrated Treatment of Cheese Whey and Hi-Tech Waste

In a global context characterized by severe environmental problems and increasing resource scarcity, waste represents both a challenge and an opportunity. This study aims to demonstrate with a real case the potential for optimizing the waste valorization action attainable through the synergic application of different treatments to residues of equally different nature and origin. In particular, bio-chemical (dark fermentation), chemical-physical (selective leaching) and thermo-chemical (hydrothermal carbonization) treatments were applied for the integrated valorization of whey from sheep cheese production and Hi-Tech waste (discarded electrical and electronic equipment). The treatments were applied at a laboratory scale on real samples of these residues. The organic acids used for selective leaching of valuable metals from Hi-Tech waste were obtained by dark fermentation of the cheese whey, while hydrothermal carbonization was used to convert the waste from previous stages into hydrochar feasible as solid fuel or soil improver. The dark fermentation tests have highlighted the possibility of recovering ≈ 100 g of organic acids from 1 L of whey; furthermore, it is also possible to recover bio-hydrogen depending on the operating conditions applied and the type of targeted organic acids. The leaching tests have demonstrated how the organic acids from whey fermentation have selective and quantitative mobilization capacities comparable to those of the same acids available on the market. The carbonization tests produced carbon-enriched hydrochar with promising fuel properties, as well as process waters suitable for anaerobic digestion with methane production. The results of the project led to the filing of an international patent

A comparison among bio-derived acids as selective eco-friendly leaching agents for cobalt: the case study of hard-metal waste enhancement

Peculiar chemical, mechanical, and magnetic properties make cobalt a key metal for a variety of “hot” applications like the cathode production of Li-ion batteries. Cobalt is also the preferred metallic binder for tungsten carbide tool manufacturing. The recent increasing criticality of cobalt and tungsten is driving the interest of manufacturers and researchers toward high-rate recycling of hard-metal (HM) waste for limiting the demand for raw materials. A simple and environmentally friendly hydrometallurgical route for Co-selective dissolution from HM wastes was developed by using weak, bio-derived, and biodegradable organic acids (OAs). In this study, OAs, namely, acetic (HAc), citric (H3Cit), maleic (H2Mal), lactic (HLac), succinic (H2Suc), lactobionic (HLB), and itaconic (H2It) acids, were selected for their pKa1 values spanning from 1.8 to 4.7 and systematically tested as selective cobalt leaching agents from WC-Co-based wastes in water, isolating the formed complexes in the solid state. Thereby, all of them seemed to be efficient in selective Co leaching, achieving almost quantitative Co dissolution from HM by-products still at low concentration levels and room conditions in a short time, leaving the residual WC unreacted and ready to be re-employed for industrial purposes. Nevertheless, two main categories of organic acids were distinguished depending on their oxidizing/complexing behavior: class 1 OAs, where the metal oxidation is carried out by H+, and class 2 OAs, where oxidation is carried out by an external oxidant like O2. A combined experimental/theoretical investigation is described here to show the reasons behind this peculiar behavior and lay the foundation for a wider discussion on the leaching capabilities of OAs toward elemental metals. Due to the demonstrated effectiveness, low cost, eco-friendliness, and large availability through biotechnological fermentative processes, particular attention is devoted here to the use of HLac in hydrometallurgy as an example of class 2 OA. WC-Co materials recovered by HLac mild hydrometallurgy demonstrated a metallurgical quality suitable for re-employment in the HM manufacturing process

A new facile solvometallurgical leaching method for the selective Co dissolution & recovery from hard metals waste

Hard Metals (HM) production plays a fundamental role in economy and technological development. Due to the criticality of its main raw materials, W and Co, a sustainable HM waste recycling is hence desirable for both environmental and economic reasons and strongly encouraged by European waste management directives. This work describes a new solvometallurgical leaching method based on diluted maleic acid (H2Mal) ethanolic solutions, which demonstrated to couple effectiveness in materials enhancement from HM waste, with mildness and sustainability of operative conditions. Specifically, H2Mal (0.5 M, EtOH) selectively and quantitatively leached Co trapped within WC-Co powders, to afford [Co(HMal)2(H2O)4] complex within 4 h at room temperature and leaving WC unreacted and ready for re-employment in HM manufacturing. Characterization of the resultant materials i.e. treated powders (SEM-EDS, p-XRD, ICP-OES) and Co-leaching solutions (ICP-OES), confirmed the near quantitative Co removal as well as the possibility to finely tune the composition of WC-Co mixtures. Parameters for best leaching conditions, i.e. time and liquid-to-solid ratio, were obtained. A scale-up experiment addressed to test the leaching conditions and the quality of the recycled material is also described. The quality of the recycled material for direct re-employment in HM manufacturing was validated by Metallurgical Quality Control, to good effect. Finally, preliminary experiments on cobalt metal recovery from the metal complex by electrowinning and by quantitative precipitation as CoCO3 were performed with encouraging results: a step forward resources circularity