Development of a thermochemical/biological process to convert waste biomass into new resources

The increasing attention to environmental issues of recent times encourages us to find new methods for the production of energy from renewable sources, and to improve existing ones, increasing their energy yield. Most of the waste and agricultural residues, with a high content of lignin and non-hydrolysable polymers, cannot be effectively transformed into biofuels with existing technology. The purpose of the study was to develop a new thermochemical/ biological process (named Py-AD) for the valorization of scarcely biodegradable substances. A complete continuous prototype was design built and run for 1 year. This consists into a slow pyrolysis system coupled with two sequential digesters and showed to produce a clean pyrobiogas (a biogas with significant amount of C2-C3 hydrocarbons and residual CO/H2), biochar and bio-oil. Py-AD yielded 31.7% w/w biochar 32.5% w/w oil and 24.8% w/w pyrobiogas. The oil condensate obtained was fractionated in its aqueous and organic fraction (87% and 13% respectively). Subsequently, the anaerobic digestion of aqueous fraction was tested in a UASB reactor, for 180 days, in increasing organic loading rate (OLR). The maximum convertible concentration without undergoing instability phenomena and with complete degradation of pyrogenic chemicals was 1.25 gCOD L digester-1 d-1. The final yield of biomethane was equal to 40% of the theoretical yield and with a noticeable additional production equal to 20% of volatile fatty acids. The final results confirm that anaerobic digestion can be used as a useful tool for cleaning of slow pyrolysis products (both gas and condensable fraction) and the obtaining of relatively clean pyrobiogas that could be directly used in internal combustion engine.

Theoretical and experimental investigations on homologation of ethanol to butanol using a ruthenium-based catalyst

The mechanism of homologation of bioethanol to butanol and higher alcohols via the Guerbet reaction was computationally and experimentally investigated. The catalytic pathway involves a ruthenium-based complex and a base co-catalyst which work simultaneously. Due to selectivity issues, secondary products were formed and high competition between main pathway and side reactions was recorded. Herein, the overall catalytic mechanism for all the processes involved in was investigated, also considering the principal side reactions, using density functional theory (DFT) methods and experiments to confirm theoretical outcomes. Due to the complexity of the reaction network, kinetic simulations were established from DFT results, confirming experimental products distribution and giving insights into the factors governing the reaction mechanism.