Co-pyrolysis of lignin and polyethylene with the addition of transition metals - Part I: Thermal behavior and kinetics analysis

In order to realize a promissing disposal of solid wastes, especially for biomass and plastics, and the recovery of high value-added products, lignin (LG) and polyethylene (PE) were co-pyrolyzed with the addition of transition metals. Thermal behavior and kinetics of the mixtures affected by the type of transition metals (0.5 mmol/g Ni, Co, Fe and Mn), the concentration of Ni (0–1 mmol/g Ni), the ratio of LG to PE (4:1-1:4) and heating rate (10–40 °C/min) were investigated according to thermogravimetric analysis (TGA). It is found that the treatment of LG/PE with 0.5 mmol/g Ni, Co, Fe or Mn results in the decrease of the initial decomposition temperature of LG and PE in the mixture by 10–53 °C and 9–18 °C, respectively. According to the difference of weight loss (ΔW), the introduction of Fe and Mn has slight influences on the interaction between LG and PE while a negative effect of PE on the devolatilization of LG in LG/PE can be largely diminished with the involvement of Ni and Co. Kinetic analysis reveals that the pyrolysis of LG and PE can be well fitted by a single first order model reaction while two consecutive first order model reactions are needed to exactly describe the co-pyrolysis of LG/PE with or without transition metals. The E value of LG and PE in the mixture is reduced by 6.11–21.62 kJ/mol and 7.67–50.11 kJ/mol, respectively, when 0.5 mmol/g Ni, Co, Fe or Mn was involved. Moreover, the concentration of Ni, the ratio of LG to PE and the heating rate play important roles on the thermal behavior and kinetics of the co-pyrolysis of LG/PE.