Multiscale Thermodynamic and Exergetic Assessment of Tri-Reforming of Methane for CO₂ Valorization and Process Intensification

Tri-reforming of methane (TRM) has emerged as a promising pathway for low-carbon syngas production by integrating steam reforming, dry reforming, and partial oxidation within a single process. This coupling enables simultaneous CH₄ utilization and CO₂ valorization while enabling internal heat generation and flexible adjustment of the H₂/CO ratio for downstream synthesis. However, TRM performance cannot be adequately evaluated using conversion or energy efficiency alone, because the process involves complex interactions among competing reaction pathways, transport phenomena, catalyst stability, and thermodynamic irreversibility. This review provides a multiscale critical assessment of TRM from both first-law energy and second-law exergy perspectives, linking reaction-network fundamentals to reactor-level behavior and system-level performance. The literature evidence shows that although high temperatures and near-autothermal operation can enhance CH₄ conversion and reduce external heat demand, these conditions may simultaneously intensify deep oxidation, hotspot formation, carbon-forming tendencies, and exergy destruction. While equilibrium analyses help define feasible operating windows, they are insufficient without kinetic modeling and reactor-scale studies that capture spatial non-uniformities and pathway competition. Across reported TRM systems, exergy destruction is consistently concentrated within the reformer, identifying the reacting core as the dominant thermodynamic bottleneck. Accordingly, the key challenge in TRM is not simply to maximize conversion but to preserve chemical work potential while maintaining syngas quality and operational stability. Viewed from this perspective, TRM is better understood as an irreversibility-aware multiscale design problem in which optimal performance depends on the integrated optimization of catalyst functionality, reactor architecture, heat management, and system-level operation.