On the use of hydrogen peroxide in diesel autothermal reforming

Abstract

As the global demand for clean hydrogen continues to rise, efficient methods for its production are critical for decarbonizing energy systems. This study investigates the direct utilization of hydrogen peroxide (H₂O₂) as an oxidant in diesel autothermal reforming (ATR), leveraging its dual role as both an oxidant and an intrinsic heat source, which is particularly advantageous in oxygen-limited environments. While prior studies have primarily focused on H₂O₂ decomposition as a heat source and oxygen supply, its direct use without pre-decomposition throughout the reforming process remains underexplored. This work provides experimental and computational evaluations of H₂O₂-driven ATR, comparing catalytic (PFR) and sequential (PSR + PFR) reactor configurations. Results demonstrate that reforming efficiency, H₂ yield, and H₂ selectivity increase with temperature and H₂O₂ concentration. At 600 °C, H₂ production reaches 22.7 %, while reforming efficiency reaches 84.7 %, significantly higher than 56.6 % for oxy-steam. Similarly, at 50 wt% H₂O₂, H₂ selectivity improves to 46 %, whereas oxy-steam achieves only 11.7 %. The catalytic configuration (PFR) consistently outperforms the sequential configuration (PSR + PFR). The rapid decomposition of H₂O₂ provides an immediate heat source, accelerating reaction onset and improving reforming efficiency and H₂ selectivity. While simulations effectively capture hydrogen production trends, discrepancies in CO and C₂H₄ predictions highlight limitations in kinetic models and reactor assumptions. These findings emphasize the need for refined modeling approaches while confirming H₂O₂'s potential as a versatile oxidant for advancing clean hydrogen production.