This study investigates iron acetylacetonate (Fe(acac)₃) as a catalyst for enhancing high-temperature oxidation (HTO) during in situ combustion (ISC) of heavy oil. Thermal analysis revealed that Fe(acac)₃ decomposes at 360 °C to form crystalline magnetite (Fe₃O₄). This transformation precedes the HTO regime. Differential scanning calorimetry demonstrated significantly intensified HTO reactions in catalytic systems, as peak temperatures were lower than those in non-catalytic reactions. Kinetic analysis showed that the catalyst reduces HTO activation energy by 15.6%, substantially increasing reaction rates across the HTO temperature range. X-ray powder diffraction confirmed that the mixed-valence Fe²⁺/Fe³⁺ configuration in the magnetite structure facilitates electron transfer during oxidation, enabling more complete combustion at lower temperatures. These findings represent a novel approach to catalyst design, from general activity to temperature-specific activation for a more stable and efficient in situ combustion process.

In this research work, the catalytic performances of two manganese-based catalysts, manganese (III) acetylacetonate (Mn(acac)3) and manganese tallate (Mn-TO), were studied during the process of Ashalcha heavy oil oxidation under in situ combustion conditions. DSC analysis shows distinct thermal behavior of both ligated catalysts during low- and high-temperature oxidation phases (LTO and HTO); for example, the shifting in peak temperature (Tp) in the HTO at a heating rate of 10 °C/min was reduced by approximately 5.3% for Mn-TO and 2.24% for Mn(acac)3 when compared with uncatalyzed heavy oil. Combined isothermal kinetic analyses using the Friedman and Kissinger–Akahira–Sunose analytic methods have provided insights about activation energies and frequency factors over the whole conversion range, where the catalytic performance of Mn-TO showed low activation energies in both LTO and HTO (E_α of Mn-TO was approximately 13.33% (LTO) and 7.68% (HTO) less than with the heavy oil alone). In addition, calculations of the effective rate constant confirmed the increased oxidation rate trend of both catalysts, with Mn-TO exhibiting the highest values. The findings highlight the potential of these manganese-based catalysts, the Mn-TO catalyst in particular, in optimizing heavy oil oxidation processes. The overall results further contribute to developing more efficient ligand catalyst complexes for sustainable heavy oil recovery while continuously improving their efficient application during in situ combustion in the petroleum industry.