In-situ combustion (ISC) is a promising thermal enhanced oil recovery (EOR) method for heavy oils. However, its field application is still limited due to difficulty in ignition, low combustion efficiency, unstable combustion front, etc. To improve the success rate of ISC process, we investigated the effectiveness of copper-based oil soluble catalyst for catalyzing combustion and in-situ upgrading of heavy oils.
High-pressure differential scanning calorimetry (HP-DSC) and TGA were used to investigate the effect of catalyst on the thermochemistry (onset temperature, temperature range of reaction interval, heat effect, etc.) and kinetic parameters of combustion process. A Porous medium thermo-effect cell (PMTEC) was designed to study the catalytic combustion of heavy oil in porous media under air flow. And, a visual combustion tube (VCT) was developed to study the catalytic effect of catalyst on the ISC process, including improving combustion front propagation, in-situ upgrading of heavy oils, and oil recovery.
HP-DSC results showed that copper-based oil soluble catalyst significantly shifted the low-temperature oxidation (LTO), transition stage (FD), and high-temperature oxidation (HTO) into lower temperature ranges. Especially for HTO, the end temperature was decreased about 120 °C. It was finished at a narrower temperature region with a higher heat flow, which implies that the combustion efficiency of HTO was greatly improved. TG-DTG data also showed the combustion reaction was transferred into lower temperatures. In addition, from TG-DTG and kinetic data, it can be concluded that the catalyst significantly reduced the activation energy in FD and HTO stage, which thus decreases the reaction barriers between FD and HTO and increases the continuity of reactions between FD and HTO.
PEMTC experiments also showed that the ignition temperature of heavy oil combustion in porous media in airflow was decreased about 46 °C by copper-based catalyst. VCT experiments indicated that in the presence of copper-based oil soluble catalyst, combustion front propagate faster, oil recovery was 10% higher than without catalyst, and a deep in-situ oil upgrading was achieved with a significant viscosity reduction (9 times lower) and increase of saturates content (especially alkanes with lower carbon number C11-C17). All these results showed that copper-based oil soluble catalyst has a great potential in improving the efficiency of ISC process and in-situ oil upgrading. Its application can help to improve the success rate and wide application of ISC process for heavy oil recovery, which will promote the highly efficient development of heavy oil resources.
Oil-dispersed
α-Fe2O3 nanocatalysts
were prepared by coating α-Fe2O3 nanoparticles
with oleic acid (OA). Mössbauer spectroscopy, X-ray diffraction,
and field emission scanning electron microscopy were used to characterize
α-Fe2O3 and α-Fe2O3@OA. Their impact on the oxidation process of heavy oil was
evaluated using a porous medium thermo-effect cell and thermogravimetry–infrared
spectroscopy coupled with isoconversional kinetic analysis. Compared
with α-Fe2O3, α-Fe2O3@OA more efficiently catalyzed the combustion of heavy oil
due to its good dispersion in heavy oil. α-Fe2O3 was found to be transformed into smaller size magnetite (Fe3O4), maghemite (γ-Fe2O3), and α-Fe2O3 during heavy oil combustion.
Fe2O3@OA reduced the activation energy from
a maximum of 537 to 246 kJ/mol, which considerably facilitates fuel
formation and makes an easier transition from fuel formation to its
combustion in the high-temperature oxidation (HTO) stage, thus shifting
HTO into lower temperatures. These enhanced performances in the heavy
oil combustion by α-Fe2O3@OA could be
favorable for improving the efficiency of the in situ combustion (ISC)
technique in oilfields.
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