Heterogeneous Solid Acid Catalysts for the Hock Cleavage of Cumene Hydroperoxide: Mechanism, Catalyst Design, and Industrial Perspectives

The cleavage of cumene hydroperoxide (CHP) via the Hock rearrangement is a cornerstone process in the chemical industry, responsible for over 90% of global phenol and acetone production. Despite its industrial significance, the conventional use of homogeneous sulfuric acid catalysis presents critical drawbacks, including severe equipment corrosion, generation of hazardous waste, and the need for complex neutralization steps. This review explores the transition toward heterogeneous solid acid catalysts as a sustainable alternative, emphasizing the relationship between catalyst structure, surface acidity, and reaction performance. Key catalyst families—such as ion-exchange resins, zeolites, and heteropolyacids—are systematically evaluated, with a focus on how Brønsted acid site density and porous architecture influence catalytic activity and selectivity. Particular attention is given to deactivation mechanisms, including coking, leaching of active species, and poisoning by inorganic cations, alongside mitigation strategies enabled by rational catalyst design and regeneration protocols. Additionally, we highlight recent progress in reactor engineering, particularly the integration of solid acid catalysts in reactive distillation and microchannel configurations. These insights offer a strategic perspective for developing more efficient and environmentally benign industrial processes for the Hock cleavage of cumene hydroperoxide.