Use of In-Situ ESR Measurements for Mechanistic Studies of Free Radical Non-Catalytic Thermal Reactions of Various Unconventional Oil Resources and Biomass.

The exhaustion of conventional light oils necessitates the shift towards unconventional sources such as biomass, heavy oil, oil shale, and coal. Non-catalytic thermal cracking by a free radical mechanism is at the heart of the upgrading, prior to refining into valuable products. However, thermal pyrolysis is hindered by the formation of asphaltenes, precursors to coke, limiting cracking, causing equipment fouling, and reducing product stability. Free radicals are inherently present in heavy fractions and are generated during thermal processes. This makes these reactive intermediates central to understanding these mechanisms and limiting coking. Electron spin resonance (ESR) spectroscopy facilitates such mechanistic studies. Over the past decade, there has been no review of using in-situ ESR for studying thermal processes. This work begins with a brief description of free radicals' chain reactions during thermal reactions and the wealth of information ESR provides. We then critically review the literature that uses ESR for mechanistic studies in thermal pyrolysis of biomass, heavy oil, shales, and coal. We conclude that limited literature exist, and more investigations are necessary. The key findings from existing literature are summarized to know the current state of knowledge. We also explicitly highlight the research gaps.