Autoxidation of aromatics

Autoxidation is a conversion pathway that has the potential to add value to multinuclear aromatic-rich coal liquids, heavy oils and bitumens, which are typically considered low-value liquids. In particular, autoxidation of these heavy materials could lead to products that may have petrochemical values, e.g., lubricity improvers and emulsifiers. Proper assessment of an oxidative transformation to ring-open the multinuclear aromatics present in heavy feeds relies on the understanding of the fundamentals of aromatic oxidation. This work reviews the selective oxidation chemistry of atoms that form part of an aromatic ring structure using oxygen (O-2) as oxidant, i.e., the oxidation of aromatic carbons as well as heteroatoms contained in an aromatic ring. Examples of industrially relevant oxidations of aromatic and heterocyclic aromatic hydrocarbons are provided. The requirements to produce oxygenates involving the selective cleavage of the ring C-C bonds, as well as competing non-selective oxidation reactions are discussed. On the other hand, the Clar formalism, i.e., a rule that describes the stability of polycyclic systems, assists the interpretation of the reactivity of multinuclear aromatics towards oxidation. Two aspects are developed. First, since the interaction of oxygen with aromatic hydrocarbons depends on their structure, oxidation chemistries which are fundamentally different are possible, namely, transannular oxygen addition, oxygen addition to a carbon-carbon double bond, or free radical chemistry. Second, hydrogen abstraction is not necessary for the initiation of the oxidation of aromatics compared to that of aliphatics.