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. 2024 Dec 24;30(1):10.
doi: 10.3390/molecules30010010.

Analysis of the Pyrolysis Kinetics, Reaction Mechanisms, and By-Products of Rice Husk and Rice Straw via TG-FTIR and Py-GC/MS

Li Lin  1 , Yang E  1 , Qiang Sun  1 , Yixuan Chen  2 , Wanning Dai  3 , Zhengrong Bao  3 , Weisheng Niu  4 , Jun Meng  1
Affiliations

Analysis of the Pyrolysis Kinetics, Reaction Mechanisms, and By-Products of Rice Husk and Rice Straw via TG-FTIR and Py-GC/MS

Li Lin et al. Molecules. .

Abstract

This study employed thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) to characterize and provide insights into the pyrolysis behaviors and by-products of rice husk (RH) and rice straw (RS). The primary pyrolysis range is partitioned into three stages, designated as pseudo-hemicellulose, pseudo-cellulose, and pseudo-lignin pyrolysis, by an asymmetric bi-Gaussian function. The average activation energies of the three pseudo-components of RH were estimated by the Flynn-Wall-Ozawa and Starink methods to be 179.1 kJ/mol, 187.4 kJ/mol, and 239.3 kJ/mol, respectively. The corresponding values for RS were 171.8 kJ/mol, 185.8 kJ/mol, and 203.2 kJ/mol. The results of the model-fitting method indicated that the diffusion model is the most appropriate for describing the pseudo-hemicellulose reaction. The reaction of pseudo-cellulose and pseudo-lignin is most accurately described by a nucleation mechanism. An accelerated heating rate resulted in enhanced pyrolysis performance, with RS exhibiting superior performance to that of RH. RH produces 107 condensable pyrolysis by-products, with ketones, acids, and phenols representing the largest proportion; RS produces 135 species, with ketones, phenols, and alcohols as the main condensable by-products. These high-value added by-products have the potential to be utilized in a variety of applications within the agricultural, bioenergy, and chemical industries.

Keywords: Py-GC/MS; TG-FTIR; kinetics; master plot method; pyrolysis; rice residues.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
TG and DTG curves of biomass pyrolysis at five heating rates: (a) RH and (b) RS; TG and DTG curves of biomass pyrolysis at 20 °C/min: (c) RH and (d) RS; deconvolution of the devolatilization phase at 20 °C/min: (e) RH and (f) RS.
Figure 2
Figure 2
(a–c) FWO plot and (d–f) Starink plot for the three subphases of RH.
Figure 3
Figure 3
(a–c) FWO plot and (d–f) Starink plot for the three subphases of RS.
Figure 4
Figure 4
Comparison of G(α)/G(0.5) versus conversion for the three substages of (a–c) RH and (d–f) RS with reaction modeling at 20 °C/min.
Figure 5
Figure 5
G(α) versus EaP(x)/βR for the three substages of biomass pyrolysis: RH (a–c) and RS (d–f).
Figure 6
Figure 6
Comparison of the calculated values of the three substages of (a–c) RH and (d–f) RS with experimental data at five heating rates.
Figure 7
Figure 7
Infrared spectra of pseudo-component peaks: RH (a) and RS (b).
Figure 8
Figure 8
Gas emissions from RH and RS pyrolysis and their peak absorbance results. (a): H2O, (b): CH4, (c): CO2, (d): CO, (e): NO, (f): C=O, (g): NO2, (h): Aromatics, (i): C-O.
Figure 9
Figure 9
(a) Yields of gases from RH and RS pyrolysis; (b) relative yields of organic pyrolysis by-products from RH and RS.
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