Improved method for kinetic parameters estimation of non-isothermal reaction: Application to residuum thermolysis

The kinetic study on thermal reaction of heavy oil at high temperature generally employs the batch reactor. The effect of non-isothermal reaction, occurring at the heating and cooling period of the experiment, is necessary to be taken into account. Otherwise, it will make differences between the calculated and experimental values. Furthermore, the temperature variation is non-linear, which causes difficulty for kinetic parameter estimation of the complex reaction network. An estimation method for kinetic parameters of non-isothermal reaction with non-linear temperature variation is developed in this paper, based on the equivalent reaction temperature. The derivation and numerical verification of this method are presented. A parallel kinetic model and a 3-lump parallel-series kinetic model of residuum are employed to investigate the validity of this method. Results show that this method is suitable for nth-order parallel reaction and simple first-order parallel-series reaction, and it can be used in kinetic studies of biomass, oil shale and other thermo-sensitive materials at high temperature.