Mechanistic insights into the effects of biopolymer conversion on macroscopic physical properties of waste activated sludge during hydrothermal treatment: Importance of the Maillard reaction

Abstract

In this study, the molecular transformation of sludge biopolymers during hydrothermal treatment with the temperature ranging from 25 °C to 200 °C was examined and was seen to significantly affect the macrophysical properties (dewaterability and rheological property) of sludge. The results showed that the sludge dewaterability and flow ability under high shear stress deteriorated by a hydrothermal process at 25 °C to 120 °C, but the deterioration alleviated above the temperature threshold of 120 °C. The consistence of changes in sludge dewaterability and rheological property in HT process was mainly attributed to the variation in gel properties of soluble biopolymer. Two-stage changes in biopolymer transformation were identified, beginning with a solubilization stage from 25 °C to 120 °C in which a biopolymer with a gel-like network structure was released into liquid phase, creating flow resistance under high shear stress such that sludge dewaterability deteriorated. The second stage was identified as a conversion stage (120 °C–200 °C) in which proteins and polysaccharides hydrolyzed and experienced a Maillard reaction, leading to the degradation of the biopolymer network structure. The newly formed recalcitrant Maillard products showed weak flow response to high shear stress, allowing for an improvement in sludge dewaterability. The pathways of a Maillard reaction were identified via gas chromatography−mass spectrometer (GC–MS), 1H nuclear magnetic resonance spectroscopy (1H NMR) and two-dimensional correlation spectral analysis (2D-COS) of Fourier-transform infrared spectrometer (FTIR), etc. Three-dimensional excitation-emission matrix (3D-EEM) proved to be an applicable method for tracking Maillard reaction in sludge hydrothermal process due to the distinctive fluorescence characteristics of Maillard products. This study further clarifies the obscure process of sludge hydrothermal treatment and will help improve the accuracy of subsequent research.