Molecular composition of hydrothermal liquefaction wastewater from sewage sludge and its transformation during anaerobic digestion

•Ultrahigh resolution mass spectrometry was applied to characterize the HTLWWs.•Biopolymers (HMW PS and PN) were the most refractory sub-fractions during AD process.•Recalcitrant compounds, like nitrogenous compounds were identified. Anaerobic digestion (AD) has shown potential to convert hydrothermal liquefaction wastewater (HTLWW) into biogas in previous studies. However, the identification of refractory components and further insights into the molecular transformations of organics in HTLWW are essential for developing more efficient AD processes. In this study, two HTLWWs were obtained from the temperature-derived hydrothermal liquefaction of sewage sludge at 170 ℃ and 320 ℃. Their molecular compositions, as well as their modifications in the subsequent AD process, were characterized using a suite of advanced molecular tools. The dissolved organic matter (DOM) in the high temperature-derived HTLWW was lower in molecular weight, less saturated, less oxidized, and enhanced in nitrogenous substances. During the AD process, most of the volatile compounds and low molecular weight (LMW) neutrals were removed, while biopolymers were the most refractory. Carboxylic-rich alicyclic molecules (CRAM), particularly those containing 3 to 5 N for low temperature-derived DOM and 1 to 3 N for high temperature-derived DOM, were resistant to anaerobic biodegradation. Meanwhile, compounds with fewer nitrogens and more carboxyl groups were preferentially produced. This molecular characterization of HTLWW-derived DOM and examination of its transformation during AD will contribute to the development of efficient methods for HTLWW treatment in the future.