Kinetic study of the pyrolysis of pine cone shell through non-isothermal thermogravimetry: Effect of heavy metals incorporated by biosorption

The study concerns the pyrolysis kinetics of exhausted pine cone shell after its use as biosorbent of copper and lead from aqueous solutions in a fixed bed column. First, breakthrough curves of biosorption process were obtained. Main dynamic biosorption parameters were determined and analyzed. Then, non-isothermal thermogravimetric experiments were carried out with raw and metal-loaded biomass in a thermobalance under nitrogen atmosphere at different heating rates. A comparative study was performed. The activation energy dependent on the conversion rate was estimated by Flynn-Wall-Ozawa (a free integral or iso-conventional method) and a mechanistic model (an integral or model-fitting method that considers three independent parallel reactions). The fluctuation of activation energy in Flynn-Wall Ozawa model can be considered the result of thermal degradation reactions of different pseudo-components of the lignocellulosic material (hemicellulose, cellulose and lignin). For raw pine cone shell and metal-loaded-pine cone shell, best fit parameters were determined according to a three independent parallel reactions scheme. The copper and lead present in metal-loaded samples did not modify values of determined parameters which describe the pyrolysis process. Finally, chemical analysis of the chars indicated that about 95% and 99% of copper and lead presented on original waste was recovered in generated chars.