Studies on the evolution of asphaltene structure during hydroconversion of petroleum residues

Abstract

The evolution of asphaltenes has been studied under hydroconversion conditions with an ebullated bed on a Buzurgan (Middle East) feedstock. A bench unit was used to produce effluents in residue conversion conditions ranging from 55 to 85 wt.%. In those conditions, asphaltene conversion ranged 62–89 wt.%. Asphaltenes from the feedstock and unconverted asphaltenes have been characterized using Size Exclusion Chromatography to evaluate asphaltene size, and 13C Nuclear Magnetic Resonance to evaluate the evolution of the average molecular structure parameters of asphaltenes. Results obtained were compared to results obtained at moderate residue conversion levels in a fixed bed. The work clearly shows that unconverted asphaltene evolution is continuous. Unit size decreases with increasing conversion while the aromaticity of the asphaltenes increases due to dealkylation. Our results suggest that the remaining asphaltenes are dissociated in smaller aggregates around 50% conversion. Below this level, asphaltene evolution may be related to dissociation mechanisms. Above 50% conversion, the chemical structure of asphaltene units still significantly evolves through dealkylation mechanisms, leading to fairly condensed structures that remain at high conversion. Based on these results, an attempt was conducted to interpret the evolution of unconverted asphaltenes as a function of residue conversion level using a simple molecular reconstruction method.