Hollow ZSM-5 encapsulated with single Ga-atoms for the catalytic fast pyrolysis of biomass waste

The development of efficient metal-zeolite bifunctional catalysts for catalytic fast pyrolysis (CFP) of bio-mass waste is highly desirable for bioenergy and renewable biofuel production. However, conventional metal-loaded zeolites often suffer from metal sintering during pyrolysis and are thus inactivated. In this study, single-site Ga-functionalized hollow ZSM-5 (GaOx@HS-Z5) was synthesized via an impregnation-dissolution-recrystallization strategy without H2 reduction. The Ga atom was coordinated to four oxygen atoms in HS-Z5 frameworks. Benefitting from the highly dispersed single-Ga atoms and hollow zeolite framework, 3GaOx@HS-Z5 performed the best in producing hydrocarbon-rich bio-oil compared to impregnated 3GaOx/HS-Z5 and H2-reduced 3Ga@HS-Z5 in the maize straw CFP. In particular, 3GaOx@HS-Z5 delivered the highest bio-oil yield (23.6 wt%) and hydrocarbon selectivity (49.4 area%). 3GaOx@HS-Z5 also retained its structural integrity and catalytic activity after five pyrolysis-regeneration cycles, demonstrating its advantage in practical biomass CFP. The elimination of H2 reduc-tion during the synthesis of catalyst provides an additional advantage for simplifying the CFP process and reducing operating costs. The retained Ga micro-environment and anti-sintering properties were unique for 3GaOx@HS-Z5, as severe metal sintering occurred during pyrolysis for other metals (e.g., NiOx, ZnOx, FeOx, and CoOx) that encapsulated HS-Z5. & COPY; 2023 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.

Automated summary

The development of efficient metal-zeolite bifunctional catalysts is crucial for bioenergy and renewable biofuel production. In this study, a Ga-functionalized hollow ZSM-5 catalyst was synthesized without H2 reduction and showed excellent performance in catalytic fast pyrolysis (CFP) of maize straw. The catalyst exhibited high bio-oil yield and hydrocarbon selectivity, and retained its structural integrity and catalytic activity after multiple regeneration cycles. The elimination of H2 reduction simplifies the CFP process and reduces operating costs.