The aim of this work is to implement an efficient and robust optimization approach for parameter estimation of pyrolysis kinetic model to study the pyrolysis of a typical agricultural residue. Thermogravimetric profiles of rape straw were obtained at a wide heating range of 10, 20, 30 and 40 degrees C/min in an inert atmosphere of nitrogen and the thermal decomposition process was studied in detail. First, three different kinetic methods (Friedman, KAS and OFW) were applied for activation energy determination. The activation energies ranged from 191.16 kJ/mol to 264.31 kJ/mol. Then, the reaction mechanism and pre-exponential factor were analyzed by using the generalized master-plots method. It is found that at conversion level higher than 0.4 the rape straw decomposition was governed by 3-D diffusion model and it tended to high order reaction model at lower conversion. Finally, a multi component parallel reactions scheme incorporated into the Particle Swarm Optimization (PSO) technique was presented to determine kinetic parameters. The kinetic triplets and other stoichiometric parameters were optimized against profiles for heating rates of 20 and 30 degrees C/min. The optimized activation energy value is 156.41 kJ/mol, 211.26 kJ/mol and 57.84 kJ/mol for hemicellulose, cellulose and lignin, respectively. These results are in conformity with results reported in previous literatures. Meanwhile, the obtained pre-exponential factors values also lie in the reasonable range of lnA(i) = 25.32-39.14 In/s according to intrinsic transition-state theory. Furthermore, cross-validated results show that the optimized parameters can be applied not only to conditions where they were obtained, but also to conditions beyond (10 and 40 degrees C/min), indicating that the derived results are appropriate to simulate and predict rape straw pyrolysis under various heating rates, which will be useful for further design and sizing of biomass thermochemical process reactors. (C) 2017 Elsevier Ltd. All rights reserved.