Plastic waste gasification using oxygen-enriched air and steam: Experimental and model results from a large pilot-scale reactor.

Advanced thermochemical technologies for plastic waste valorization represent an interesting alternative to waste-to-energy options. They are particularly appealing for waste-to-hydrogen and waste-to-chemicals applications, with autothermal steam-oxygen gasification in fluidized bed reactors showing the greatest market potential. The study describes a series of experimental tests carried out on a large pilot-scale fluidized bed gasifier, using steam and O2-enriched air, with increasing fractions of oxygen. Different values of the main operating parameters are varied: equivalence ratio (0.22-0.25), steam-to-carbon ratio (0.7-1.13), and steam-to-oxygen ratio (up to 3.2). The fuel consists of real mixed plastic waste coming from separate collection of municipal solid wastes. The data obtained are used to investigate in depth the role of the main operating parameters and to improve and validate a recently developed one-dimensional kinetic model for waste gasification. The validation shows a good agreement between experimental data and model results, suggesting the reliability of the model to predict the reactor behavior under conditions of pure steam-oxygen gasification, relevant to many industrial applications. It has been found that the equivalence ratio is the parameter that most affects the syngas composition. At a constant equivalent ratio, the molar fraction of oxygen in the enriched air shows a limited influence on syngas composition while the steam is crucial in controlling the temperature along the reactor. Provided that the steam-to-carbon molar ratio is larger than 1.5, steam affects mainly the reactor temperature rather than the syngas composition, qualifying the steam-to-oxygen molar ratio as an instrumental parameter for smooth plant operation.

Waste-derived catalysts for tar cracking in hot syngas cleaning.

Catalytic tar cracking is a promising technique for hot syngas cleaning unit in gasification plants because it can preserve tars chemical energy, so increasing the syngas heating value. The cost associated with catalyst preparation is a key issue, together with its deactivation induced by coke deposition. Iron is a cheap and frequently used catalyst, which can also be found in some industrial wastes. The study aims to assess the catalytic efficiency for tar cracking of two waste-derived materials (red mud and sewage sludge) having high content of iron. The catalysts were supported on spheres of γ-Al2O3, and their efficiency was compared to that of a pure iron catalyst. The role of support was investigated by testing pure red mud, with and without the support. A series of long-term tests using naphthalene as tar model compound were carried out under different values of process temperatures (750 °C-800 °C) and steam concentrations (0 %-7.5 %). The waste derived catalysts showed lower hydrogen yields compared to pure iron catalyst, due to their lower content of iron. On the other hand, the conversion efficiencies of all the tested catalysts resulted rather similar, since the Alkali and Alkaline-Earth Metallic species present on the surface of waste-derived catalyst help in preventing coke deposition. The iron oxidation state appears to play an important role, with reduced iron more active than its oxidised form in the tar cracking reactions. This indicates the importance of tuning steam concentration to keep constant the reduced state of iron while limiting coke deposition.

An LCA answer to the mixed plastics waste dilemma: Energy recovery or chemical recycling?

The study focuses on mixed plastics waste (MPW), whose complex and unpredictable composition (due to high polymer heterogeneity, additives, and contaminants) makes its valorisation a true technical, environmental, economic, and regulatory challenge. Chemical recycling by means of advanced thermochemical treatments (ATT) could be a successful strategy, able to support the transition from a carbon intensive to a carbon negative sector, and alternative to the current treatments of energy recovery or mechanical downcycling. Some of these ATTs provide an efficient recovery of valuable resources, such as fuels and chemicals, but their role is mainly limited by time necessary to complete the process optimization and implement the required infrastructures. A reliable identification of the best alternatives is thus crucial. A specific LCA approach quantifies the environmental performances of a selected set of ATT technologies for resource recovery from MPW. It includes plastics-to-energy, by combustion or gasification; plastics-to-methane and plastics-to-hydrogen, by gasification; and plastics-to-oil, by thermal pyrolysis. The results highlight the crucial role of carbon capture and storage (CCS) units, which partially reduces that of the specific thermochemical treatment. The best performances, particularly for Climate Change category, are those of the MPW-to-hydrogen by gasification, followed by those of MPW-to-energy by combustion or gasification, all equipped with CCS. The sensitivity analysis considers the evolution of the European energy mix, characterised by a larger utilisation of renewable energy sources, and highlights the corresponding increased sustainability of chemical recycling by ATTs. This suggests that the MPW dilemma should be definitively solved in a close future.