Design-of-Experiments Analysis of Green Methanol Oxidative Reforming over Agglomerated Catalysts for Hydrogen Production

In this work, sustainable hydrogen production from green methanol via oxidative reforming was investigated over agglomerated Co-Cr/SBA-15 catalysts. A mixed factorial design of experiments was applied to the effects of temperature, weight hourly space velocity (WHSV), steam-to-carbon ratio (S/C), and oxygen-to-carbon ratio (O2/C) on methanol conversion and hydrogen yield. The developed models exhibited good predictive performance within the investigated operating domain. Temperature and WHSV were identified as the most influential variables for both responses, whereas increasing the S/C ratio significantly enhanced hydrogen yield. In contrast, higher O2/C ratios promoted methanol conversion, but reduced hydrogen yield due to enhanced oxidation pathways. Optimal conditions for hydrogen production were identified at 600 °C, WHSV= 30 h−1, S/C = 2, and O2/C = 0.10. Under these conditions, the agglomerated catalyst showed catalytic performance comparable to that of the powdered counterpart, confirming that shaping with bentonite does not compromise activity. Furthermore, the shaped catalyst retained approximately 95% of its initial methanol conversion after 50 h time-on-stream while maintaining an almost constant hydrogen yield, with negligible coke formation and cobalt sintering. These results demonstrate the potential of agglomerated Co-Cr/SBA-15 catalysts for hydrogen production from green methanol under the investigated oxidative steam reforming conditions and stable performance over 50 h time-on-stream.