An Analysis of the Methane Cracking Process for CO2-Free Hydrogen Production Using Thermodynamic Methodologies

The thermal cracking process of methane does not present the emissions of polluting gases, forming only hydrogen with a high degree of purity and solid carbon that can be commercialized for other industrial purposes globally. Thermodynamic methodologies based on Gibbs energy minimization and entropy maximization are used in the present study to simulate operating conditions of isothermal and adiabatic reactors, respectively. The chemical equilibrium and combined phases problem were written in a non-linear programming form and optimized with the GAMS software using the CONOPT 3 solver. The results obtained by the methodology described in this study present a good agreement with the data reported in the literature, with mean relative deviations lower than 1.08%. High temperatures and low pressures favor the decomposition of methane and the formation of products. When conditioned in an isothermal reactor, total methane conversions are obtained at temperatures above 1200 K at 1 bar. When conditioned to an adiabatic reactor, due to the lack of energy support provided by the isothermal reactor and taking into account that it is an endothermic process, high methane-conversion rates are obtained for temperatures above 1600 K at 1 bar. As an alternative, the combined effects of the addition of hydrogen to the feed combined with a system of extreme pressure variation indicate a possibility of conducting the thermal cracking process of methane in adiabatic systems. Setting the CH4/H2 ratio in the system feed at 1:10 at 1600 K and 50 bar, following severe depressurization through an isentropic valve, varying the pressure from 50 to 1 bar, the methane conversion varies from 0 to 94.712%, thus indicating a possible operational conformation for the process so that the amount of carbon generated is not so harmful to the process, taking into account that the formation of the same occurs only after the reaction and heating processes. Under the same operating conditions, it is possible to use about 40.57% of the generated hydrogen to provide energy for the process to occur.