Utilizing relatively mild hydrothermal conversion technique (under optimized conditions, 200 °C, 4 h, 1:10 solid-liquid ratio, 0.5 M NaOH), lignocellulosic biomass can be efficiently transformed into humic acids, thereby significantly enhancing its utilization. Additionally, this approach provides a means for precise manipulation of the composition and properties of the resulting humic acids. In this comprehensive study, lignocellulosic biomass, comprising various attributes like coniferous, broadleaf, and grassy species, as well as model components like cellulose, hemicellulose, and lignin, underwent hydrothermal reactions to produce humic acids. Firstly, a systematic evaluation was conducted to determine the influence of operational parameters on the formation of humic acids. Subsequently, the characteristics of humic acids derived from diverse lignocellulosic biomass sources were analyzed and benchmarked against commercial humic acids. Based on the empirical findings, a mechanistic pathway for the generation of humic acids was figured out. The results indicate that the primary stages in the hydrothermal conversion of lignocellulosic biomass to humic acids involve initial hydrolysis into smaller molecular components, followed by further reactions leading to the formation of humic acids. Notably, the interplay between cellulose, hemicellulose, lignin, and other minor components, such as tannins and pectins, plays a pivotal role in the synthesis of humic acids. The characterization of the derived humic acids revealed several noteworthy distinctions from commercial products. In the infrared spectroscopy (FTIR) and elemental analysis (EA) characterization, the synthetic humic acid has more oxygen functional groups, alkane groups and aromatic structures. In the X-ray photoelectron spectroscopy (XPS), the synthetic humic acid has more diverse forms and proportions of elements. In thermogravimetric analysis (TGA), the synthesized humic acid has higher thermal stability. The synthetic humic acid has a rougher surface microstructure. The synthetic humic acid has higher fluorescence intensity in three-dimensional fluorescence spectrum (3D EEM). Lignocellulose biomass raw materials with high wood quality content can obtain higher humic acid yield, but the interaction of cellulose, hemicellulose, lignin and other group components (such as tannins, pectin, etc.) in the hydrothermal process plays an important role in the generation of humic acid. This research offers valuable insights into the chemically driven production of humic acids and the strategic control of their properties, based on the structural and compositional nuances of the raw materials.
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