Effect of process conditions on the hydrothermal partial oxidation of phenanthrene as a heavy oil model structure

- Process conditions where higher yields to organic soluble products are obtained were determined.
- Pressure had minimum impact in conversion, but had great influence in product compositions.
- Low yields to coke were obtained at all reaction conditions studied.
- Temperature had a minor effect in the yield to gas that was mainly affected by O/Ostoich ratio.

The decline in light oil production has triggered the necessity to develop effective processes to upgrade heavy oil feedstocks. An alternative to traditional heavy oil upgrading processes is the hydrothermal partial oxidation in near-critical or supercritical conditions. Partial oxidation leads to the formation of oxygen functionalities in aromatic rings located in central positions within the molecule. These functionalities destabilize the aromatic ring structure, making it more prone to cracking reactions. In this work, the effect of pressure, the ratio between the initial oxygen loaded into the system with respect to the stoichiometric oxygen needed for total combustion (O/Ostoich ratio) and temperature were studied using phenanthrene as model compound for structures commonly found in asphaltene molecules. The process was studied at a range of pressures between 210 and 275 bar, O/Ostoich ratio from 0.1 to 0.75 and temperatures between 360 and 450 °C. Changes in pressure did not affect phenanthrene conversion, but had a great impact on product selectivities and the gas and organic-soluble fraction compositions. Increases in O/Ostoich ratio resulted in higher phenanthrene conversions and greater yields to gas. Selectivity to organic-soluble products increased with O/Ostoich ratio to find a maximum at a ratio around 0.2 to then decrease with further increments due to an increase in gas production. Any increase in temperature resulted in higher phenanthrene conversions and also higher yields to organic-soluble products. Yields to gas and coke remained low at all reaction temperatures. Higher selectivity to organic-soluble products was obtained at 230 bar, 0.2 O/Ostoich ratio and 425 °C.