Thermal degradation of xylan-based hemicellulose under oxidative atmosphere

•Xylan-based hemicellulose is tested in TG-MS under both inert and oxidative atmospheres.•Evolution of typical volatiles identified by MS is analyzed associated with the DTG curves.•A three-step consecutive kinetic model is proposed for describing thermo-oxidation of hemicellulose. Xylan-based hemicellulose sample is tested in TG-MS under He, 7% O2, 20% O2 and 60% O2, in order to underpin the understanding of thermo-degradation mechanism of hemicellulose and biomass. The mass loss history recorded by TG can be divided into two main stages: (1) low-temperature stage with the peak located at around 265°C associated with thermal cracking of hemicellulose, and (2) high-temperature stage with the peak enhanced and shifted to lower temperatures by oxygen concentration ascribed to char combustion. A number of prominently evolved ions identified by MS can be designated to acetone, acetic acid, furfural, water, CO, CO2 and so on. The releasing profile of smaller fragments (water, CO and CO2) follows the pattern of DTG curve under different oxygen concentrations (especially for that in the high temperature stage). A three-step consecutive kinetic model employing “n-order reaction function” is proposed and achieved good fit for the experimental mass loss data of thermo-oxidation of hemicellulose.