This study conducted in situ combustion oxidation experiments on crude oil from Block D within the Liaohe Oilfield, utilizing a kettle furnace low-pressure oxidation reaction method at various temperatures. The molecular composition of oxidation products was analyzed using gas chromatography–mass spectrometry (GC–MS) and high-resolution mass spectrometry. The results reveal that the molecular composition of the products remains relatively stable up to 300 °C, exhibiting a slight increase in C13-C30 alkanes. The ratio of the peak area for C21 to bisnorhopane is 0.082. From 300 °C to 450 °C, compounds with long alkyl chains gradually undergo thermal cracking, resulting in a significant increase in the production of alkanes within the C10–C30 range. The concentration of saturated hydrocarbons produced through thermal cracking reaches its maximum at a temperature of 400 °C. The most abundant peak of n-alkane is observed at C21, with a quantified ratio of peak area for C21 to bisnorhopane at 6.5, indicating a two-order magnitude increase compared to crude oil. From 500 °C to 600 °C, compounds undergo more profound thermal cracking and condensation processes. The predominant hydrocarbons consist of aromatic molecules containing two to six rings substituted with short side chains. The double bond equivalent (DBE) values of carbazoles and carboxylic acids are determined as 30 and 25, respectively. At 600 °C, the peak area ratio of naphthalene to biodecane is 300, indicating a remarkable increase of five orders of magnitude compared to the crude oil. The present study elucidates the correlation between the characteristics of combustion components in crude oil and the corresponding combustion temperature. Primary cracking reactions within crude oil are promoted effectively when keeping the combustion zone at 350 °C and 450 °C. This process significantly reduces the viscosity of heavy oil and enhances its fluidity.
