The demand for clean fuels is increasing throughout the world, with more stringent environmental regulations for transportation fuels including marine fuels, particularly regarding their sulfur content. Moreover, the quality of crude oil and derived petroleum cuts is getting lower while fossil fuels are still in high demand. Heavy oils are characterized by high sulfur content where most sulfur is found in bulky thiophenic structures difficult to remove using conventional high pressure hydrodesulfurization process. However they appeared more reactive in oxidative desulfurization (ODS) process, carried out at mild conditions without hydrogen pressure. This review focuses for the first time on the heavy fuels initially containing more than 0.5 wt.%S and upgraded by the ODS process. Different attractive approaches of the literature towards ODS are reported using homogeneous and heterogeneous catalysis. Recent developments in ODS assisted with ultrasound technology and the use of ionic liquid to enhance ODS efficiency will be fully detailed and discussed to better understand their viability when applied to high sulfur content, high viscosity, and high boiling point feeds.
The oxidative desulfurization (ODS) of heavy fuel oil (HFO) offers a promising solution for desulfurizing marine fuels under mild conditions, in line with current environmental regulations. While most studies focus on model or light fuels, explaining deactivation through leaching or sulfone adsorption, the deactivation mechanisms of catalysts in HFO remain poorly understood. In this work, Mo-based catalysts supported on alumina were extensively characterized before and after catalytic reactions, and regeneration through air calcination was considered. Techniques such as XRD, Raman spectroscopy, XRF, and TGA, alongside catalytic testing with H2O2 as an oxidant, revealed that Mo surface speciation significantly impacted both activity and deactivation. Contrary to well-dispersed polymolybdates, crystalline MoO3 induced low activity and hindered regeneration. No leaching of the active phase was demonstrated during the reaction. Sulfone adsorption had minimal impact on deactivation, while non-sulphur compounds appeared to be the key contributors. Regeneration outcomes were found to be molybdenum content-dependent: 10Mo/Al recovered its activity, while 20Mo/Al formed inactive phases, like Al2(MoO4)3. Using an organic oxidant (tBHP) during ODS influenced the regeneration, as it prevented Al2(MoO4)3 formation and redispersed crystalline MoO3, enhancing performance. These findings advance understanding of catalyst deactivation and suggest strategies to extend catalyst life in the ODS of HFO.
Inland waterway transport (IWT) needs to significantly decrease its fossil fuelconsumption and greenhouse gas emissions. To achieve this, operationaloptimization techniques are a promising approach. Among them, eco-driving aimsto provide driving instructions to minimize energy consumption. In this study, amethodology to produce a mission profile minimizing fuel consumption on a givenitinerary is presented. An energy model considering waterway restriction,current speed, and dynamic effects is proposed. Then, an optimization procedureis developed and applied using this model, allowing to determine a feasibleoptimal mission profile, with a travel time constraint. Applications to a 110mtypical inland vessel on diverse itineraries are presented, showing fuelconsumption reductions up to 12%, compared to a constant engine rotationalspeed scenario. Consideration of the strongly variable efficiency of internalcombustion engines, as well as acceleration and deceleration phases, provedgains to be possible even for an itinerary with uniform characteristics (width,depth, current speed) over its whole length. It also showed that travel timeconstraint and consideration of acceleration phases are the most influentfactors for energy optimization.
This study explores deep eutectic solvents (DESs) as potential alternatives to dimethylformamide (DMF) for extractive desulfurization of gas oil and marine fuel oil. A series of DESs, based on choline chloride (ChCl) and tetrabutylammonium bromide (TBAB), were evaluated using straight-run gas oil (SRGO) and compared to DMF. The influence of an oxidation pre-treatment and water content was also investigated, and the most efficient systems were further applied to marine fuel oil. Firstly, oxidation was found to be essential to enhance sulfur removal by improving the extractability of sulfone compounds. The results show that DES formulation strongly affects desulfurization performance, with TBAB-based DESs achieving efficiencies comparable to DMF (~80% desulfurization rate) and outperforming ChCl-based systems. In ChCl-based DESs, a moderate water content (~10 wt%) improved performance, whereas higher amounts disrupted the hydrogen-bond network, as evidenced by Fourier-transform infrared spectroscopy, leading to a decreased efficiency. When applied to marine fuel oil, similar trends were observed, although lower desulfurization levels were obtained due to the complexity of the feed, and a solvent-to-fuel ratio of 5:1 was required for proper phase separation. Fourier transform mass spectrometry analyses highlighted the persistence of refractory sulfur species, emphasizing the need for tailored solvent design. Overall, DESs represent promising and adaptable alternatives for desulfurization processes.