Energy Analysis of Hydrogen Production from Methanol under Atmospheric Pressure and Supercritical Water Conditions

Abstract

The energy analysis of hydrogen production from the methanol reforming and oxidation under atmospheric (ATM) pressure and supercritical water (SCW) conditions was performed. The equilibrium hydrogen was investigated by the minimization of the Gibbs free energy based on Peng-Robinson equation of state for high pressure and ideal gas equation for atmospheric pressure. An objective of this study was to obtain the optimum operating conditions to maximize the net hydrogen yield, defined as the hydrogen yield taking into account also the methanol consumed by combustion to generate heat. This was done by investigating the effect of operating parameters over the following ranges: temperatures between 773 and 1273 K, pressures between 0.1 and 25.0 MPa, water-to-methanol (H2O:MeOH) ratios between 1 and 5, and oxygen-to-methanol (O2:MeOH) ratios between 0 and 1.05. At ATM pressure, it was found that the equilibrium hydrogen yield increases with increasing H2O:MeOH ratio but the peak of equilibrium H2 yield is at 973 K for higher H2O:MeOH ratio than 1:1. Additionally, the total heat load increases significantly as the reaction temperature and the water amount increase. Therefore, the optimum net H2 yield is at the H2O:MeOH ratio of 2:1 and the reaction temperature at 973 K. Under SCW conditions, an increase of temperature and water amount in the system constantly increases the equilibrium H2 yield. It means that the high H2O:MeOH ratio and temperature are required in SCW. The presence of oxygen in hydrogen production was investigated that an increase of O2:MeOH ratio constantly decreases the H2 yield and also the net H2 yield for reaction at ATM pressure whereas under SCW conditions, the equilibrium H2 yield and the net H2 yield increase with increasing oxygen up to 0.42 and 0.84, respectively.