Evolution of functional group of lignocellulosic biomass and its delignified form during thermal conversion using synchrotron-based THz and laboratory-based in-situ DRIFT spectroscopy
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Date
2023-05-05
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Elsevier
Abstract
In the industry, platform chemicals are traditionally synthesized from non-renewable resources. In order to determine the ideal temperature range and associated emissions for the production of platform chemicals from biomass, which is a renewable resource, mechanistic insights into the thermochemical conversion of biomass are needed. Here, the high-resolution synchrotron-based gas-phase THz (Far-IR) spectra and lab-based in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) spectra of both raw and delignified biomass have been studied to identify real-time evolution of the functional groups and any gas-phase secondary reactions during the thermochemical conversion as a function of temperature; these are linked to weight loss measurements through differential thermogravimetry. The high-resolution synchrotron-based technique and DRIFTS were used to acquire the spectra in two different wavenumber ranges of 50–600 cm−1 and 500–4500 cm−1, respectively. The synchrotron-based spectra were used to identify the major gaseous components between 300 and 500 °C of methane, ethane, acetylene and formaldehyde, and their generation followed the order 300 > 400 > 500 °C. The DRIFTS spectra showed that the covalent hydrogen bonds of both raw and delignified biomass was cleaved below 250 °C, between 250 and 300 °C the decarboxylation reaction took place, whereas between 300 and 400 °C platform chemicals (furan, levoglucosan, levoglucosenone) and aromatic compounds were formed from the dehydration of the cellulosic part of the biomass. No changes in the DRIFTS spectra were observed above 400 °C. These results suggest that 300–400 °C is the ideal temperature range for the thermochemical conversion of biomass to platform chemicals. Pyrolysis-gas chromatography/mass spectrometry (Py-GCMS) results demonstrated that the identification of platform chemicals laid the groundwork for large-scale operation. © 2023 The Author(s). Published by Elsevier Ltd.
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Keywords
Biomass, Synchrotron radiation, Thermochemical processes, Thermal gravimetric analysis, Structural chemical analysis, Mass spectroscopy, Infrared spectra, Cellulose, Delignification
Citation
Kundu, C., Biswas, S., Thomas, B. S., Appadoo, D., Duan, A., & Bhattacharya, S. (2023). Evolution of functional group of lignocellulosic biomass and its delignified form during thermal conversion using synchrotron-based THz and laboratory-based in-situ DRIFT spectroscopy. Fuel, 348, 128579. doi:10.1016/j.fuel.2023.128579