Abstract
This review is devoted to the occurrence, extraction, structural characterization and catalytic applications of vanadyl porphyrins present in heavy crude oils and petroleum residues. Vanadyl porphyrins represent the major vanadium-containing compounds in petroleum systems and play a dual role as both catalyst poisons during refining processes and valuable precursors for functional catalytic materials. Particular attention is devoted to recent advances in extraction technologies, including solvent extraction, ionic liquids, deep eutectic solvents, functionalized adsorbents and chelating agents. Process intensification approaches such as ultrasound- and microwave-assisted extraction, are also discussed as promising strategies for improving extraction efficiency and selectivity. Furthermore, recent developments in petroleum characterization using FTICR-MS, EPR, HYSCORE and LA-ICP-MS techniques are reviewed, providing insights into metalloporphyrin speciation, oxidation states, and distribution within complex petroleum matrices. Beyond their traditional role in catalyst deactivation, vanadyl porphyrins have emerged as attractive precursors for catalytic materials applied in oxidation reactions, photocatalysis, oxidative desulfurization, wastewater treatment and selective organic synthesis. The development of hybrid catalytic systems based on mesoporous silica, graphene oxide, carbon nanotubes, polymer matrices, and metal–organic frameworks has significantly improved catalyst stability, activity and recyclability. Current challenges related to the selective extraction, preservation of metalloporphyrin structure and catalytic performance evaluation are also discussed. Overall, this review provides an integrated perspective on the recovery, characterization and valorization of vanadyl porphyrins for sustainable petroleum upgrading and environmental applications.