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This study aims to enhance the quality of biofuel through microwave torrefaction pretreatment for lignin. Low density polyethylene (LDPE) was added as a hydrogen source during microwave co-pyrolysis along with the microwave-torrefied lignin (MTL). The thermal degradation behavior and kinetic study of MTL co-pyrolysis with LDPE by microwave-assisted heating was investigated as well. The results indicated that the hydrocarbon content in the bio-oil obtained from microwave co-pyrolysis of MTL and LDPE increased significantly (about 80%). It was also noticed that the aromatic hydrocarbon content increased from 1.94% to 22.83% with the addition of LDPE. Thermal behavior analysis and reaction kinetic study showed that the addition of LDPE into MTL had the effect of promoting thermal degradation and improving reaction rate during microwave-assisted pyrolysis.