Hydrothermal upgrading of heavy oil in the presence of water at sub-critical, near-critical and supercritical conditions

Abstract

In this study, the hydrothermal upgrading (HTU) of high sulfur-content heavy oil was investigated at sub-critical (Sub-CW), near-critical (NCW) and supercritical water (SCW) conditions. Products obtained after HTU, including gases, liquid, and coke (if formed), were analyzed to understand the upgrading performance at different conditions. At Sub-CW (200, 250, and 300 °C), 250 °C is the optimum temperature where a viscosity reduction from 2073 to 1758 mPa s was achieved with a slight removal of sulfur (mainly sulfur) and the generation of a small amount of light and non-condensable hydrocarbons in gas phase (C1–C4, isoalkanes and alkenes, H2S, CO2 and H2, etc.). At NCW (350 °C) and SCW (400 °C), heavy oil was upgraded into light oil with a significant removal of heteroatoms, an increase of saturates content, a reduction of aromatics, resins and asphaltenes contents, and a high yield of light gaseous hydrocarbons (mainly methane). Simultaneously, each SARA fraction was also greatly ameliorated: the content of light alkanes with low molecular weight in saturates was increased, diaromatics content in aromatics was increased with a reduction of polyaromatics content, aromatics-type carbon atoms in resins was increased with a decrease in aliphatic hydrocarbons. Moreover, MALDI-TOF measurements of asphaltenes show that the molecular weights of asphaltenes were reduced. All these results indicated that HTU at Sub-CW can be used for heavy oil pre-treatment (in-situ or ex-situ upgrading) considering its main effect of viscosity reduction with a small removal of heteroatoms, while HTU at NCW and SWC has a great potential in in-situ and ex-situ upgrading and oil refining as it can convert heavy oil into light oil.