Integrated HRMS Data Mining Reveals Acidic Biogenic Markers in Fossil–Bio-Oil Co-Processing Products

High Resolution Image Download MS PowerPoint Slide Incorporating renewable carbon into conventional petroleum refining processes, without requiring significant investments in new infrastructure, is a promising strategy for advancing the energy transition. Among such processes, coking is a thermal cracking process that converts heavy petroleum residues into higher-value products such as diesel-range hydrocarbons. However, the introduction of renewable carbon sources, such as bio-oils, may lead to the formation of oxygenated byproducts which can promote gum formation and reduce combustion efficiency, particularly acid species such as carboxylic acids and phenols. To address these challenges and assess the feasibility of integrating renewable carbon into the coking process, slow pyrolysis bio-oil (BO) was coprocessed with vacuum residue (VR) in a coking process unit using three feed compositions (100% VR, 95% VR + 5% BO, and 90% VR + 10% BO) to evaluate the contribution of BO in coprocessing liquid products. Acidic fractions were analyzed using electrospray ionization in negative mode [ESI(−)] with Orbitrap high-resolution mass spectrometry (HRMS) to obtain a detailed chemical characterization of polar compounds. This study also employs an integrated data-mining approach using Venn diagrams and heatmaps to evaluate the detected peaks, moving beyond conventional major-class analysis. A Venn diagram approach was employed to identify ions shared between the BO and the coprocessed liquid products, indicating compounds of biogenic origin. A total of 23 ions were selected for tandem mass spectrometry (MS/MS) experiments to propose their molecular structures. The compounds were proposed as consistent with lignocellulosic-derived molecules and were grouped as carboxylic acids, methoxyphenols, hydroxybenzofurans, benzenediols, diphenols, and carbohydrates. The peak/class ratio revealed pronounced biogenic contribution, observed in the 10% BO coprocessed liquid product. The heatmaps highlight biogenic compounds with distinct distribution patterns in the HRMS data. Specifically, biogenic compounds were considered when they were not detected in the fossil matrix or showed a 2-fold increase in relative intensity upon bio-oil incorporation. Consequently, these oxygenated acidic compounds serve as specific tracers for monitoring renewable carbon content in the blends.