Hydrogen Production via the Oxy-Steam Reforming of LNG or Methane on Ni Catalysts

Ni catalysts supported on ZrO2, 5%CeO2-ZrO2, and 5%La2O3-ZrO2 were prepared via the impregnation method and tested in the oxy-steam reforming of methane and liquified natural gas (LNG). All tested catalysts exhibited high catalytic activity in the studied process at 700 and 900 degrees C. The improvement of the stability of Ni catalysts after the addition of CeO2 oxide in the studied oxy-steam reforming of LNG process was confirmed. In addition, high activity and selectivity towards hydrogen was proven in the oxy-steam reforming process at 900 degrees C over a 20%Ni/5%CeO2-ZrO2 catalyst. It was also proved that the addition of CeO2 onto a ZrO2 carrier leads to a decrease in the NiO and metallic Ni crystallite sizes that were detected by the X-Ray diffraction (XRD) technique. The solid solution formation between NiO and ZrO2 and/or NiO and CeO2 was proved. Superior reactivity in the oxy-steam reforming of CH4 and the LNG process exhibited a 20%Ni/ZrO2 catalyst, which showed the highest methane conversions at 500 and 600 degrees C, equal to 63% and 89%, respectively. In addition, also in the case of the LNG reforming reaction, the most active catalyst was the 20%Ni/ZrO2 system, which demonstrated 46.3% and 76.9% of the methane conversion value at 500 and 600 degrees C and the total conversion of others hydrocarbons (ethane, propane and butane). In addition, this catalytic system exhibited the highest selectivity towards hydrogen formation in the oxy-steam reforming of the LNG reaction equal to 71.2% and 71.3% at 500 and 600 degrees C, respectively. The highest activity of this system can be explained by the uniform distributions of Ni species and their highest concentration compared to the rest of the monometallic Ni catalysts. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) results also confirmed a strong interaction of NiO with ZrO2 in the case of the 20%Ni/ZrO2 catalysts. The presence of selected NiZrO+ ions emitted from the investigated surface of the 20%Ni/ZrO2 system was detected.