Upgrading and desulfurization of heavy oils by supercritical water

Recent work on supercritical upgrading of heavy oils is summarized within the context of other high-pressure technologies. •We present recent work on supercritical upgrading and desulfurization of oils.•Topics include reaction kinetics and mechanism, catalysis, and mixing effects.•The article concludes with recommendations for future work. Supercritical water upgrading (SCWU) of heavy oils reduces sulfur content and decreases average molecular weight, without rejecting carbon as coke products. Despite many years of industrial and academic scrutiny, many fundamental questions remain in the field: intrinsic reaction rates and mechanisms; the role of water; the need for catalysts; the importance of phase behavior and mixing. In 2009, MIT initiated a SCWU research program aimed at improving the understanding of the relevant physical, chemical, and catalytic phenomena. This overview summarizes the work performed at MIT within the historical context of SCWU with a particular focus on new kinetic rate measurements and modeling, reaction mechanism analysis, catalyst investigation, and combined mass/heat transport modeling of hydrocarbon/water mixtures. Kinetic rate measurements showed that sulfide decomposition during SCWU is consistent with a radical chain reaction pathway. Mechanistic studies and product distribution analysis identified that sulfide decomposition likely occurs via thioaldehyde and aldehyde intermediates and that water plays important roles in thioaldehyde hydrolysis (as a reactant) and aldehyde decarbonylation (as a catalyst). Catalytic investigation found that ZnO has potential to improve sulfur removal during SCWU, without addition of molecular hydrogen. Mixing studies revealed the complex dynamic processes that occur when hydrocarbons are injected into near or supercritical water. The article concludes with a summary of research needs and thoughts on the future of SCWU.