Hydrogen production from supercritical water reforming of glycerol over Ni/Al2O3–SiO2 catalyst

• Glycerol reforming using supercritical water was successfully studied over nickel catalyst.
• Hydrogen yields were very close to equilibrium values at WHSV between 1.25 and 15 gGly h−1 gCat−1.
• Ni-based catalyst allowed achieving a good process performance at 600 °C and 240 bar.
• Effect of operating variables on the process performance was explained by an original reaction pathway.

Hydrogen production from the supercritical water reforming of glycerol was studied in a tubular fixed-bed reactor by using a Ni-based catalyst supported on Al2O3 and SiO2. Tests were carried out at a pressure of 240 bar, temperatures of 500–800 °C, glycerol feed concentrations of 5–30 wt.%, and weight hourly space velocity from 1.25 to 22.5 gGly h−1 gCat−1 (residence time from 1.6 to 4.8 s through the bed). The dry gas is mainly composed of H2, CO2, CO, CH4. The results showed that the glycerol conversion was almost complete, except at the highest glycerol feed concentration and lowest temperature. Hydrogen yields were very close to those values predicted by equilibrium at a short residence time. Nickel on catalyst was completely reduced, and structured carbon nanotubes were encountered at glycerol concentrations higher than 20 wt.%. This study illustrates that the reforming of glycerol using supercritical water over a Ni catalyst makes it possible to reduce the reforming temperature needed when no catalyst is used (from 800 °C to 600 °C), achieving a high-yield hydrogen production, very close to equilibrium, and requiring less energy.