Reaction synergy of bimetallic catalysts on ZSM-5 support in tailoring plastic pyrolysis for hydrogen and value-added product production

Abstract

Hydrogen, viz. a green energy carrier, is poised to considerably contribute to the empowerment of a sustainable society. By valorizing plastics, catalytic pyrolysis was envisaged as a promising route to produce green hydrogen and value-added product here. Firstly, the screening of optimal catalyst support (from activated carbon and four zeolites: M-zeolite, B-zeolite, Y-zeolite, ZSM-5) was executed by studying catalytic polypropylene (PP) pyrolysis over supported Ni catalysts. In view of the highest H₂ yield (19.2 mmol/g_PP) of Ni/ZSM-5, ZSM-5 was put forth as the optimal catalyst support. Then, the identification of optimal active metal (from Ni, Fe, Co, FeNi, FeCo, and NiCo) was performed by running the catalytic PP pyrolysis over ZSM-5 supported catalysts. For catalytic PP pyrolysis, NiCo/ZSM-5 was the optimal catalyst with the highest H₂ yield (28.7 mmol/g_PP), while the resulting pyrolysis oil demonstrated potential for use as jet fuel. From catalytic pyrolysis of various plastics over NiCo/ZSM-5, polystyrene gave the highest H₂ composition (83.2 vol%) of pyrolysis gas and high composition (52.8 area%) of benzocyclobutene (useful chemicals for semiconductor and microelectronics fields) in pyrolysis oil. Lastly, the catalytic mechanism was discussed based on the results, revealing NiCo's remarkable enhancement in H₂ yield to 28.7 mmol/g, which surpassed the individual yields of Ni (19.2 mmol/g) and Co (10.2 mmol/g), thereby underscoring the synergistic effect of NiCo. This study supports the recycling of plastics waste into hydrogen energy and valuable products, contributing to environmental pollution mitigation.