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Distributed hydrogen generation from liquid fuels has attracted increasing attention in the past years. Petroleum-derived fuels with already existing infrastructure benefit from high volumetric and gravimetric energy densities, making them an interesting option for cost competitive decentralized hydrogen production.In the present study, direct steam reforming of diesel and diesel blends (7 vol.% biodiesel) is investigated at various operating conditions using a proprietary precious metal catalyst. The experimental results show a detrimental effect of low catalyst inlet temperatures and high feed mass flow rates on catalyst activity. Moreover, tests with a desulfurized diesel–biodiesel blend indicate improved long-term performance of the precious metal catalyst. By using deeply desulfurized diesel (1.6 ppmw sulfur), applying a high catalyst inlet temperature (>800 °C), a high steam-to-carbon ratio (S/C = 5) and a low feed mass flow per open area of catalyst (11 g/h cm2), a stable product gas composition close to chemical equilibrium was achieved over 100 h on stream. Catalyst deactivation was not observed.

Recently, liquid biofuels have attracted increasing attention as renewable feedstock for hydrogen production in the transport sector. Since the lack of hydrogen infrastructure and distribution poses an obstacle for the introduction of fuel cell vehicles to the market, it is reasonable to consider using liquid biofuels for on-board or on-site hydrogen generation. Biodiesel offers the advantage of being an environmentally friendly resource while also having high gravimetric and volumetric energy density.The present study constitutes an experimental investigation of biodiesel steam reforming, the main emphasis of which is placed on finding optimum operating conditions in order to avoid catalyst deactivation. Temperature was varied from 600 °C to 800 °C, pressure from 1 bar to 5 bar and the molar steam-to-carbon ratio from 3 to 5. Based on the experimental results, coke formation and sintering are identified as the main deactivation mechanisms. Initiation of catalyst deactivation primarily depends on catalyst inlet temperature and feed mass flow per open area of catalyst. By using a metallic based precious metal catalyst, applying low feed flow rates (31 g/h∙cm2) and a sufficiently high catalyst inlet temperature (>750 °C) coking can be minimized, thus avoiding catalyst deactivation. A stable product gas composition close to chemical equilibrium has been achieved over 100 h with a biodiesel conversion rate of 99%.