Study on the Pyrolysis Kinetic Behaviors of Different Vegetable-Tanned Sheepskin Leathers

The pyrolysis behaviors of leathers tanned with hydrolyzable tannins (Tara and Chestnut extracts), and condensed tannins (Quebracho and Mimosa extract) were studied by Thermogravimetric (TG) analysis in the present work. The TG/derivative thermogravimetry (DTG) results showed that the thermal stability of Tara- and Chestnut-tanned samples is poorer than that of Quebracho- and Mimosa-tanned ones. In order to study pyrolysis kinetics, TG experiments at different heating rates were carried out. Two methods of Flynn-Wall-Ozawa (FWO) and Friedman (FR) were employed to calculate the pyrolysis activation energy (Eα) of the samples. It was found that the average Eα of the vegetable-tanned samples is located at the range of 191.7-206.1 kJ/mol. The thermodynamic parameters (pre-exponential factor, Gibbs free energy, enthalpy, and entropy) of the samples were subsequently calculated based on the average Eα by the FR method. The Gibbs free energies of the Chestnut-, Tara-, Quebracho-, and Mimosa-tanned leathers were 176.9 kJ/mol, 179.8 kJ/mol, 179.3 kJ/mol, and 178.2 kJ/mol, respectively. The difference between the average enthalpies and the Eα is less than 5 kJ/mol, which indicated that the pyrolysis process is conductive to the product formation. The mean entropy (ΔS) of the four vegetable-tanned samples is all positive, which suggested that the pyrolysis of the samples could easily take place. This work might provide theoretical guidance for the optimization of vegetable-tanned leather waste pyrolysis.