Pyrolysis of Lignins:  Experimental and Kinetics Studies

Lignins are generally used as a low grade fuel in the pulp and paper industry. In this work, pyrolysis of Alcell and Kraft lignins obtained from the Alcell process and Westvaco, respectively, was carried out in a fixed-bed reactor and in a thermogravimetric analyzer (TGA) using helium (13.4 mL/min/g of lignin) and nitrogen (50 mL/min/g of lignin), respectively. The reaction temperature was increased from 300 to 1073 K, while the heating rates were varied from 5 to 15 K/min. The gaseous products mainly consisted of H 2, CO, CO 2, CH 4, and C 2+ . With increase in heating rate from 5 to 15 K/min both lignin conversion and hydrogen production increased from 56 to 65 wt % and from 25 to 31 mol %, respectively for fixed-bed pyrolysis reaction of Alcell lignin at 1073 K, whereas at the same condition the conversion and hydrogen production increased from 52 to 57 wt % and from 30 to 43 mol % for Kraft lignin. The distributed activation energy model (DAEM) was used to analyze complex reactions involved in the lignin pyrolysis process. In this model, reactions are assumed to consist of a set of irreversible first-order reactions that have different activation energies. This model was used to calculate the activation energy, E, the distribution of activation energy f ( E ), and the frequency factor k 0 for the pyrolysis of Alcell and Kraft lignins in a thermogravimetric analyzer (TGA). For the pyrolysis in TGA, the activation energies for Kraft and Alcell lignins varied from 129 to 361 kJ/mol with maximum distribution at ∼250−270 kJ/mol and from 80 to 158 kJ/mol with maximum distribution at ∼118−125 kJ/mol, respectively.