Enhanced hydrogen production from biomass: A dual-bed catalytic pyrolysis-reforming strategy using dolomite and perovskite

Biomass represents a promising carbon-neutral resource, yet its utilization for hydrogen production is hindered by inherent drawbacks such as high tar yield and the limited efficiency of single-catalyst systems. To address this, we developed a novel dual-bed fixed-bed reactor for the synergistic pyrolysis and steam reforming of biomass. Calcined dolomite in the pyrolysis zone facilitated primary tar cracking and in-situ CO2 capture, increasing the equivalent mass loss rate from 65.5% to 80.3%. Downstream, a tailored Co-doped LaFeO3 perovskite (LaFe0.4Co0.6O3) served as the reforming catalyst. Comprehensive characterization revealed that this optimal catalyst possessed the highest concentration of bulk oxygen vacancies, crucial for enhancing lattice oxygen mobility and the water-gas shift reaction. This integrated configuration achieved a remarkable total gas yield of 56.1 mmol/g of dry biomass. Furthermore, the system exhibited exceptional stability, sustaining an average H2 yield of 47.35 vol% over five catalytic cycles with 96.21% activity retention. Analysis of the spent catalyst indicated the in-situ formation of a protective La2CoO4 surface phase, which likely contributed to the stability by preserving the active bulk structure. This work effectively mitigates the limitations of perovskite catalysts and provides a viable, scalable foundation for efficient and durable biomass-derived hydrogen production.