Lumped kinetic modelling of polyolefin pyrolysis: a non-isothermal method to estimate rate constants

The measurement of kinetic parameters in the pyrolysis of polyolefins requires the use of a lumped kinetic model for predicting the product distribution of wax, oil and gas yields. A non-isothermal method was established, in which a sample is heated in a tube reactor to a desired temperature at a constant rate of temperature rise. This method avoided the error present in the heating up stage which is inherent in any practical isothermal method in which reaction proceeds to a significant extent before the operating temperatures of polyolefin pyrolysis are reached, which results in challenges when defining the reaction time. The non-isothermal measurements were conducted between 450 and 550 °C for polypropylene (PP) and polyethylene (HDPE and LDPE) and the temperature and lump yields are non-linearly regressed to achieve the kinetic parameters. The measured kinetic rate constants have the same trend as those reported in the literature using the isothermal method, but are lower than the values reported at similar conditions. The kinetic parameters derived are then validated by using isothermal experimental data. The calculated data using the measured kinetic parameters are generally in agreement with the experimental data. The non-isothermal method established in this work proves to be a much faster method for the measurement of intrinsic rate constants at high temperatures.