Exploration of browning reactions during alkaline thermal hydrolysis of sludge: Maillard reaction, caramelization and humic acid desorption

The browning reaction produces melanoidins, 5-hydroxymethylfurfural (HMF) and humic acids which influence subsequent anaerobic digestion and protein recovery. This paper systematically evaluates the variation of organics that make sludge browning with heating temperature and reaction time, the effect of browning organics on protein recovery and anaerobic digestion, and finally proposes a pathway for the occurrence of the Maillard reaction (MR) in the sludge environment. The results show that the browning of sludge hydrolysate is related to the comprehensive influence of the MR, caramelization and humic acid desorption. The increase of temperature (80 °C–150 °C) and pH (9–13) will promote the extent of browning of sludge hydrolysate, and the sludge browning reaction basically stabilizes at the reaction time of 1 h. Humic acid and melanoidin could co-precipitate with the protein, thereby reducing the purity of the recovered protein. The inhibition of anaerobic digestion starts when the melanoidin concentration is 8.01 mmol/L. The three-dimensional fluorescence, GC-MS and FT-IR analysis show that melanoidins have the same functional groups and fluorescence properties as humic acid does, and the humic acid in the supernatant of the sludge treated with ATH was not only converted at its adsorbed state, but also possibly generated by the reaction of the dissolved proteins with polysaccharides. Finally, LC-MS/MS was used to identify the intermediate products of the MR and the possible structural formula of melanoidin. This study further clarifies the browning reaction in hydrothermal sludge treatment and provides help for the accuracy of subsequent studies.