Oil
oxidation reactions have attracted considerable interest in
terms of mechanism comprehension for thermally enhanced oil recovery
applications. Many hypotheses regarding oil oxidation mechanisms appear
to be disputable even now. The aim of our work was to broaden current
knowledge on the crude oil oxidation chain reaction mechanism including
the formation behavior of free radicals and hydroperoxides. In this
context, we attempted to shed light on the main differences in the
oxidation reactions between heavy and light oils. We have found a
way to solve both analytically and numerically a set of differential
equations for concentrations corresponding to the reaction scheme.
Taken together, our findings allowed us to obtain hydroperoxide concentration
dependence on time for the initial stages of oxidation. Two main time
dependencies were observed, one for low-temperature oxidation (LTO)
and the other for high-temperature oxidation (HTO). Both dependencies
were revealed in the oxidation experiments of different types of oils
and were taken for the matching procedure, which is also presented
in this work. The φ-factor of branched-chain reactions, obtained
as a combination of reaction rates, determines the efficiency of LTO
and transition from LTO to HTO. By matching the experimental data,
we were able to find that the success of self-ignition may be achieved
only if the concentration ratio of saturated hydrocarbons to inhibitors
in crude oil is equal to 2 or more and the temperature is more than
415 K. Under these conditions, the ignition time for heavy oil was
5–7 days, and that for light oil was 15–30 min in oxidation
experiments, which were well matched by the presented chain reaction
model.