Thermal degradation and kinetic studies of redwood (Pinus sylvestris L.)

In this scientific paper, thermochemical conversion of redwood (RW) was studied. Using the thermogravimetric analysis' technique (TGA), the thermal behavior of RW samples was examined at four heating rates ranging from 5 to 20 K min⁻¹ in inert atmosphere between 300 and 900 K. Two main objectives have been set for this study; the first one was the determination of the kinetic decomposition parameters of RW (Pinus sylvestris L.), and the second one was the study of the variation of characteristic parameters from the TG-DTG curves of the main RW's components, such as; cellulose, hemicellulose and lignin. The kinetic analysis was performed using three isoconversional methods (Vyazovkin (VYA), Friedman (FR) and Flynn-Wall-Ozawa (FWO)), Avrami theory method and the Integral master-plots (Z(x)/Z(0.5)) method to estimate activation energy (E ₐ), reaction order (n), pre-exponential factor (A) and model kinetic (f(x)) for the thermal decomposition of cellulose, hemicellulose and lignin components. The DTG and TG curves showed that three stages identify the thermal decomposition of RW, the first stage corresponds to the decomposition of hemicellulose and the second stage corresponds to the cellulose, while the third stage corresponds to the lignin's decomposition. For the range of conversion degree (x) investigated (0.1 ≤ x ≤ 0.7), the mean values of apparent activation energies for RW biomass were 127.60–130.65 KJ mol⁻¹, 173.74–176.48 KJ mol⁻¹ and 197.21–200.36 KJ mol⁻¹ for hemicellulose, cellulose and lignin, respectively. Through varied temperatures from 550 to 600 K for hemicellulose, from 600 to 650 K for cellulose and from 750 to 800 K for lignin, the corresponding mean values of reaction order (n) were 0.200 for hemicellulose, 0.209 for cellulose and 0.047 for lignin. The pre-exponential factor's average values for three components of RW ranges from 0.08 × 10¹² s⁻¹ to 2.5 × 10¹² s⁻¹ (A ₕₑₘᵢcₑₗₗᵤₗₒₛₑ = 1.09 × 10¹² s⁻¹), 0.10 × 10¹⁴ s⁻¹ to 0.28 × 10¹⁴ s⁻¹ (A cₑₗₗᵤₗₒₛₑ = 0.17 × 10¹⁴ s⁻¹) and 3.07 × 10¹⁶ s⁻¹ to 3.69 × 10¹⁶ s⁻¹ (A ₗᵢgₙᵢₙ = 3.33 × 10¹⁶ s⁻¹), respectively. The experimental data of RW had overlapped the D ₄, D ₂ and F ₃ in the conversion degree of 10–30%, 30–55% and 55–70% for the three components, respectively.