In this paper, we analyze the autothermal reforming (ATR) of methane through Gibbs energy minimization and entropy maximization methods to analyze isothermic and adiabatic systems, respectively. The software GAMS^® 23.9 and the CONOPT3 solver were used to conduct the simulations and thermodynamic analyses in order to determine the equilibrium compositions and equilibrium temperatures of this system. Simulations were performed covering different pressures in the range of 1 to 10 atm, temperatures between 873 and 1073 K, steam/methane ratio was varied in the range of 1.0/1.0 and 2.0/1.0 and oxygen/methane ratios in the feed stream, in the range of 0.5/1.0 to 2.0/1.0. The effect of using pure oxygen or air as oxidizer agent to perform the reaction was also studied. The simulations were carried out in order to maintain the same molar proportions of oxygen as in the simulated cases considering pure oxygen in the reactor feed. The results showed that the formation of hydrogen and synthesis gas increased with temperature, average composition of 71.9% and 56.0% using air and O₂, respectively. These results are observed at low molar oxygen ratios (O₂/CH₄ = 0.5) in the feed. Higher pressures reduced the production of hydrogen and synthesis gas produced during ATR of methane. In general, reductions on the order of 19.7% using O₂ and 14.0% using air were observed. It was also verified that the process has autothermicity in all conditions tested and the use of air in relation to pure oxygen favored the compounds of interest, mainly in conditions of higher pressure (10 atm). The mean reductions with increasing temperature in the percentage increase of H₂ and syngas using air under 1.5 and 10 atm, at the different O₂/CH₄ ratios, were 5.3%, 13.8% and 16.5%, respectively. In the same order, these values with the increase of oxygen were 3.6%, 6.4% and 9.1%. The better conditions for the reaction include high temperatures, low pressures and low O₂/CH₄ ratios, a region in which there is no swelling in terms of the oxygen source used. In addition, with the introduction of air, the final temperature of the system was reduced by 5%, which can help to reduce the negative impacts of high temperatures in reactors during ATR reactions.

The supercritical water gasification (SCWG) and carbon dioxide gasification of agro-industrial and urban waste residues—Coffee Husk, Eucalyptus Biochar, Energy Sugarcane, and Refuse-Derived Fuel (RDF)—were studied using TeS^® v.2 software, which employs a non-stoichiometric thermodynamic model to minimize Gibbs free energy and predict equilibrium compositions. The effects of temperature (873.15–1273.15 K), pressure (220–260 bar), biomass feed (18–69%), and gasifying agents on hydrogen and methane formation were analyzed. Higher temperatures and biomass feed percentages favored hydrogen production, while lower temperatures increased methane formation. At 1273.15 K, RDF showed the highest hydrogen yield in SCWG, rising from 0.43 to 1.42 mol, followed by Energy Sugarcane (0.39 to 1.23 mol), Coffee Husk (0.34 to 0.74 mol), and Eucalyptus Biochar (0.33 to 0.62 mol). In CO₂ gasification, hydrogen yields were lower but followed a similar trend. At 873.15 K, RDF also exhibited the highest methane increase in SCWG, from 0.14 to 0.91 mol, followed by Energy Sugarcane (0.12 to 0.65 mol), Coffee Husk (0.11 to 0.36 mol), and Eucalyptus Biochar (0.11 to 0.29 mol). Methane formation in CO₂ gasification was significantly lower, with RDF increasing from 0.0035 to 0.35 mol, followed by Energy Sugarcane (0.0024 to 0.24 mol), Coffee Husk (0.0002 to 0.058 mol), and Eucalyptus Biochar (0.0002 to 0.028 mol). On the other hand, a slight increase in hydrogen formation was observed as pressure decreased, while the opposite effect was observed for methane formation, with a small increase in its production as pressure increased. The impact of pressure change on the equilibrium compositions was not as significant as the effect observed by varying temperature; this behavior was observed in both gasification processes studied. Additionally, the behavior of the H₂/CO molar ratio for each biomass in the studied gasification processes was analyzed to assess the potential uses of the produced syngas. It was observed that the SCWG resulted in significantly higher H₂/CO molar ratios compared to CO₂ gasification.