A Comparative Thermodynamic and Kinetic Analysis of Methane Tri-Reforming for Syngas Production: A Process Simulation Approach
DOI:
https://doi.org/10.18041/1794-4953/avances.1.13283Keywords:
DWSIM, chemical equilibrium, catalytic reactor, computational simulation, methane tri-reforming, process simulation, reaction kinetics, syngas, thermodynamic analysisAbstract
The growing concentration of greenhouse gases, primarily methane (CH₄) and carbon dioxide (CO₂), underscores the need for advanced carbon capture and utilization (CCU) technologies. Methane tri-reforming (TRM) has emerged as a highly promising pathway for the valorizitation of these gases, converting them into syngas (a mixture of H₂/CO), which serves a critical feedstock for the chemical industry. This study develops and applies a comprehensive process simulation framework to systematically evaluate the TRM process, addressing a notable gap in the literature regarding the rigorous comparison between thermodynamic limits and actual kinetic performance under different feed compositions. Using the DWSIM process simulator (version 8.1.2), a comparative analysis was conducted employing two distinct reactor models: a Gibbs reactor model to determine thermodynamic equilibrium limits and a kinetic Plug Flow Reactor (PFR) model to assess performance under practical conditions. The investigation evaluated three different feed compositions, varying the molar ratios, with the objective of identifying optimality criteria based on: (1) maximum combined conversion of CH₄ and CO₂, (2) suppression of coke formation, (3) efficient production of adjustable syngas, and (4) favorable energy balance. The thermodynamic analysis identified an optimal operating window between 800 K and 900 K at atmospheric pressure, where reactant conversions are maximized and secondary coke-forming reactions are suppressed. The kinetic analysis revealed that an ideal feed composition (molar fractions of: CH₄= 0,545, CO₂ =0,182, H₂O =0,091) achieves a methane conversion of 33,0% and produces syngas with an H₂/CO molar ratio of 3,0 at 800 K, representing the best compromise between conversion and selectivity. Finally, thermal and composition profiles along the reactor were evaluated, demonstrating syngas formation and the accelerated methane consumption during the tri-reforming process. This work provides a robust computational methodology for optimizing TRM feed conditions and producing syngas with tunable compositions, offering valuable insights for the conceptual design and scale-up of reactors for sustainable chemical production.
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