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Abstract

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.

Abstract

In this paper, thermal degradation (TGA) and pyrolysis studies of sunflower shell biomass (SSB), eucalyptus biomass (EB), wheat straw biomass (WSB), and peanut shell biomass (PSB) were carried out using the thermogravimetric analysis and stainless steel tubular reactor. Thermal degradation of all biomass wastes was examined at a heating rate of 10 °C/min in nitrogen atmosphere between 20 and 800 °C. Experiments of pyrolysis were carried out in a tubular reactor from 300 to 700 °C with a heating rate of 10 °C/min, a particle size of 0.1–0.3 mm and nitrogen flow rate of 100 mL.min⁻¹, which the aim to study how temperature affects liquid, solid, and gas products. The results of this work showed that three stages have been identified in the thermal decomposition of SSB, EB, WSB, and PSB wastes. The first stage occurred at 120–158 °C, the second stage, which corresponds to hemicellulose and cellulose's degradation, occurred in temperatures range from 139 to 480 °C for hemicellulose, and from 233 to 412 °C for cellulose, while the third stage occurred at 534–720 °C. It was concluded that temperature has a significant effect on product yields. The maximum of bio-oil yields of 37.55, 30.5, 46.96, and 50.05 wt% for WSB, PSB, SSB, and EB, were obtained at pyrolysis temperature of 500 °C (SSB, PSB, and WSB) and 550 °C (EB). Raw biomass, solid and liquid products obtained were characterized by elemental analysis, Fourier transformed infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR), and x-ray diffraction (XRD). The analysis of solid and liquid products showed that bio-oils and bio-chars from agricultural biomass wastes could be prospective sources of renewable fuels production and value added chemical products.