Evolution of gaseous contaminants from biomass pyrolysis has drawn increasing attention. However, the thermal degradation, dynamics, and synergetic evolution mechanisms during real-time biomass pyrolysis remain unclear. Herein, a novel method using thermogravimetry-Fourier transform infrared spectrometry-gas chromatography/mass spectrometry (TG-FTIR-GC/MS) combined with thermal kinetics and two-dimensional correlation spectroscopy was proposed to explore the chemical properties and temperature response mechanisms of gaseous species released during Phragmites communis (PC) and Typha angustifolia (TA) pyrolysis. The thermal degradation mechanisms of PC/TA pyrolysis were mainly associated with the sigmoidal rate and random nucleation mechanisms. The formation intensities of alcohols/ethers, phenols/esters, acids, aldehydes, and ketones were higher during low-temperature TA pyrolysis and high-temperature PC pyrolysis. The average carbon oxidation state () of gaseous species mainly ranged from -1.5 to -0.5, and the slope of most gaseous species was greater than -2.0, which was related to the reduction of aldehyde/ketone groups. Two-dimensional (2D)-TG-FTIR-COS analysis revealed that the sequential temperature response of gaseous species followed: acids → phenols, esters → aldehydes → hydrocarbons → alcohols, ethers → aromatics during PC/TA pyrolysis. The establishment of relationships between the sequential response of gases and degraded components provides an important basis for online monitoring/recovery of gaseous contaminants during biomass pyrolysis.
Keywords: evolution mechanism; gas emission; real-time biomass pyrolysis; synchronous and asynchronous maps.