Ni–Sr/TiZr for H 2 from methane via POM: Sr loading & optimization

Achieving remarkable H2 yield with significantly high H2/CO over Ni-based catalysts through partial oxidation of methane (POM) is a realistic approach to depleting the concentration of CH4 and using H2 and CO as synthetic feedstock. This study examined Ni catalysts on titania–zirconia for methane conversion via POM at 600 °C and atmospheric pressure. The addition of strontium to the catalyst was explored to improve its performance. Catalysts were characterized by X-ray diffraction, Raman-infrared-UV-vis spectroscopy, and Temperature-programmed reduction-desorption techniques (TPR, TPD). 2.5 wt% Sr addition induced the formation of the highest concentration of extreme basic sites. Interestingly, over the unpromoted catalyst, active sites are majorly generated by hardly reducible NiO species whereas upon 2.5 wt% promoted Sr promotional addition, most of active sites are derived by easily reducible NiO species. 45% CH4 conversion and 47% H2 yield with H2/CO = 3.5 were achieved over 2.5 wt% Sr promoted 5Ni/30TiO2 + ZrO2 catalyst. These results provide insight into the role of basic sites in enhancing activity through switching indirect pathways over direct pathways for POM. Further process optimization was carried out in the range of 10 000–22 000 SV, 0.35–0.75 O2/CH4, and 600–800 °C reaction temperature over 5Ni2.5Sr/30TiO2 + ZrO2 by using central composite design under response surface methodology. The optimum activity as high as ∼88% CH4 conversion, 86–87% yield of H2, and 2.92H2/CO were predicted and experimentally validated at 800 °C reaction temperature, 0.35O2/CH4 ratio, and 10 000 space velocity

The role of ceria in promoting Ni catalysts supported on phosphate‐modified zirconia for the partial oxidation of methane

The catalytic partial oxidation of methane (POM) is aimed at the mitigation of CH4 (a highly potent greenhouse gas) from the environment and the synthesis of syngas with a high H2/CO ratio. Herein, to enhance the POM reaction, Ni-supported phosphate-modified-zirconia were synthesized with promotor “Ce” to achieve high H2/CO ratio (2.4–3.2). The catalysts were characterized by surface area and porosity, X-ray diffraction, RAMAN, temperature-programmed experiments (TPR, CO2-TPD, and TPO), and TEM. Increasing the ceria addition over 10Ni/PO4 + ZrO2 resulted in lower crystallinity, higher dispersion of active sites, and enhanced the surface area of catalyst. The unique and prominent reducibility and basicity of NiO-species and surface oxide ions, respectively, are particularly notable at 4 wt.% ceria loading. At a reaction temperature of 600°C, the highest concentration of active sites and a unique concentration of moderate strength basic sites can be achieved with 4 wt.% ceria loading over 10Ni/PO4 + ZrO2. This leads to 44% conversion of CH4, 36% yield of H2, 35% yield of CO2, and H2/CO ratio of 3.16 for the POM reaction. The cyclic H2TPR-O2TPO-H2TPR experiment confirms the reorganization of the active site towards high temperature under oxidizing gas O2 and reducing gas H2 gas stream during the POM reaction.<br/