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The thermal behavior and kinetic study of lignocellulosic biomass (rice straw (RS)) and linear low-density polyethylene (LLDPE) pyrolysis over modified ZSM-5 catalyst were investigated using thermo-gravimetric analysis (TGA). Cellulose and lignin were used as model compounds of biomass in order to investigate the reaction mechanism of lignocellulosic biomass and polyethylene co-pyrolysis. Results showed that RS&LLDPE co-pyrolysis was more complicated than that of the individual components. The activation energy (E) of RS, and RS&LLDPE pyrolysis were 79.61kJ/mol and 59.70kJ/mol respectively, suggesting that there was a positive synergistic interaction between RS and LLDPE. The addition of LLDPE with lignin co-pyrolysis obtained a lower apparent activation energy (33.39kJ/mol) compared to raw lignin pyrolysis (53.10kJ/mol). Results indicated that the Cobalt modified ZSM-5 catalyst was able to improve the reaction rate of RS and LLDPE co-pyrolysis; also the addition of Co/ZSM-5 catalyst resulted in a lower apparent activation energy during cellulose and LLDPE co-pyrolysis., (Copyright © 2017 Elsevier Ltd. All rights reserved.)