Experimental characterization of hydrogen containing flames

The current environmental and socio-economic situation promotes the development of carbon-neutral and sustainable solutions for energy supply. In this framework, the use of hydrogen has been largely indicated as a promising alternative. However, safety aspects are of concern for storage and transportation technologies. Indeed, the current know-how promotes its transportation via pipeline as compressed gas. However, the peculiar properties of hydrogen make the selection of suitable materials challenging. For these reasons, dilution with less reactive species has been considered a short and medium solution. As a way of example, methane-hydrogen mixtures are currently transported via pipelines. In this case, the hydrogen content is limited to 20% in volume, thus keeping the dependence on natural gas sources. On the contrary, hydrogen can be conveniently transported by mixing it with carbon dioxide deriving from carbon capture and storage technologies. In this sense, the interactions between hydrogen and carbon dioxide have been poorly studied. In particular, the effects of composition and operative conditions in the case of accidental release or for direct use in the energy supply chain are unknown. For these reasons, the present work was devoted to the characterization of the chemical phenomena ruling the system. To this aim, laminar flames containing hydrogen and carbon dioxide in the air were investigated experimentally and numerically. Different detailed kinetic mechanisms largely validated were considered at this stage. Significant discrepancies were observed among numerical and experimental data, especially once a fuel consisting of 40%v of hydrogen was studied. This deviation was attributed to the formation of a cellular flame increasing the overall reactivity. Hence, this observation suggests the need for combined models accounting for peculiar physical phenomena and detailed kinetic mechanisms characterizing the hydrogen-containing flames.

Theoretical and experimental study on the role of benzoquinone in the Guerbet reaction catalyzed by a ruthenium complex

The benzoquinone was found as an effective co-catalyst in the ruthenium/NaOEt-catalyzed Guerbet reaction. The co-catalyst behavior has therefore been investigated through experimental and computational methods. The reaction products distribution shows that the reaction speed is improved by the benzoquinone supplement since the beginning of the process, having a minimal effect on the selectivity toward alcoholic species. DFT calculations were performed to investigate two hypotheses for the kinetic effects: i) a hydrogen storage mechanism or ii) a basic co-catalysis of 4-hydroxiphenolate. The most promising results were found for the latter hypothesis, where a new mixed mechanism for the aldol condensation step of the Guerbet process involves the hydroquinone (i.e. the reduced form of benzoquinone) as proton source instead of ethanol. This mechanism was found to be energetically more favorable than an aldol condensation in absence of additive, suggesting that the hydroquinone derived from benzoquinone could be the key species affecting the kinetics of the overall process. To verify this theoretical hypothesis, new phenol derivatives were tested as additives in the Guerbet reaction. The outcomes confirmed that an aromatic acid (stronger than ethanol) could improve the reaction kinetics. Lastly, theoretical products distributions were simulated and compared to the experimental one, using the DFT computations to build the kinetic models.

Experimental and numerical characterization of flame instability in hydrogen-containing flames

In the framework of the energy transition, the acquisition of proper knowledge of fundamental aspects characterizing the use of alternative fuels is paramount as well as the development of optimized know-how and technologies. In this sense, the use of hydrogen has been indicated as a promising route for decarbonization at the end-users stage in the energy supply chain. However, the elevated reactivity and the low-density at atmospheric conditions of hydrogen pose new challenges. Among the others, the dilution of hydrogen with carbon dioxide from carbon capture and storage systems represents a possible route. However, the interactions between these species have been poorly studied so far. For these reasons, this thesis, in collaboration between the University of Bologna and Technische Universität Bergakademie of Freiberg in Saxony (Germany), investigates the laminar flame of hydrogen-based premixed gas with the dilution of carbon dioxide. An experimental system, called a heat flux burner, was adopted ad different operating conditions. The presence of the cellularity phenomenon, forming the so-called cellular flame, was observed and analysed. Theoretical and visual methods have allowed for the characterization of the investigated flames, opening new alternatives for sustainable energy production via hydrogen transformation.