An Integrated Thermodynamic-Exergy-Kinetic Framework for Dry Reforming of Methane, Using Gibbs Energy Minimization with Peng-Robinson EOS and Mechanistic Rate Modeling.

Dry reforming of methane (DRM) has attracted significant attention as a pathway for the simultaneous utilization of CH4 and CO2 to produce synthesis gas for low-carbon fuel and chemical production. This thesis develops an integrated modeling framework that combines equilibrium thermodynamics, real-gas behavior, exergy analysis, multi-objective optimization, and experimentally validated reaction kinetics. A Gibbs free-energy minimization approach coupled with the Peng–Robinson equation of state was employed to predict equilibrium compositions, syngas quality, and carbon formation limits over practical operating conditions. Second-law analysis demonstrates that operating conditions maximizing reactant conversion do not necessarily minimize thermodynamic irreversibility. To address these competing objectives, a composite desirability-based optimization framework was formulated, incorporating conversion performance, carbon suppression, and exergy efficiency. A detailed kinetic model was subsequently developed and calibrated using experimental data obtained over a Ni–Ce MOF-derived catalyst. Among ten candidate rate expressions, an irreversible dual-site Langmuir–Hinshelwood formulation yielded the best agreement with experimental observations (𝑅2 = 0.9904), indicating distinct activation pathways for CH4 and CO2. The combined thermodynamic, exergy, and kinetic analyses consistently identify an optimal operating windownear 900Kat a CH4/CO2 feed ratio close to unity, where high conversion, elevated exergy efficiency, and minimal carbon formation are simultaneously achieved. The methodology developed in this work provides a thermodynamically grounded and industrially relevant basis for the design and optimization of DRM-based syngas processes.