Literature Review on Thermodynamic and Kinetic Limitations of Thermal Decomposition of Methane

The state of the art in methane pyrolysis does not yet provide a definitive answer as to whether the concept of an elementary reaction is universally applicable to the apparently simple process of methane dissociation. Similarly, the literature currently lacks a comprehensive and unambiguous description of the methane pyrolysis process and, in particular, a single model that would well represent its course at both the micro and macro scales. Given the wide range of conditions under which this reaction can occur—whether thermal or thermo-catalytic, in solid or fluidized bed reactors—it is crucial to evaluate the usefulness of different kinetic models and their compatibility with basic thermodynamic principles and design assumptions. To address these research gaps, the authors analysed the thermodynamic and kinetic dependencies involved in the thermal decomposition of methane, using the synthesis of methane from its elemental components and its reversibility as a basis for exploring suitable kinetic models. Using experimental data available in the literature, a wide range of kinetic models have been analysed to determine how they all relate to the reaction rate constant. It was found that regardless of whether the process is catalytic or purely thermal, for temperatures above 900 °C the reversibility of the reaction has a negligible effect on the hydrogen yield. This work shows how the determined kinetic parameters are consistent with the Kinetic Compensation Effect (KCE) and, by incorporating elements of Transition State Theory (TST), the possibility of the existence of Entropy–Enthalpy Compensation (EEC). The indicated correspondence between KCE and EEC is strengthened by the calculated average activation entropy at isokinetic temperature ( ∆ S B = − 275.0 J · ( m o l · K ) − 1 ) . Based on these results, the authors also show that changes in the activation energy ( E = 20 – 421 k J · m o l − 1 ) can only serve as an estimate of the optimal process conditions, since the isoconversion temperature ( T i s o = 1200 − 1450 K > T e q ) is shown to depend not only on thermodynamic principles but also on the way the reaction is carried out, with temperature (T) and pressure (P) locally compensating each other.