Organic Acids for Lignin and Hemicellulose Extraction from Black Liquor: A Comparative Study in Structure Analysis and Heavy Metal Adsorption Potential

This study presents a method for extracting lignin and hemicellulose from black liquor using organic acids (citric, malic, and acetic) in comparison to the traditional sulfuric acid method. We investigated and compared the influence of the acid type on the structural properties of the resulting precipitates in the context of their potential applications. The lignin fractions were characterized for their chemical structure (ATR-FTIR, NMR), thermal stability (TGA), morphology and surface elemental composition (SEM-EDS), bulk elemental composition (C, H, N, S), and molecular weight distribution (GPC). The hemicellulose fractions were analyzed for their molecular weight (GPC), surface elemental composition (EDS), and chemical structure (ATR-FTIR). These analyses revealed subtle differences in the properties of the individual materials depending on the extraction method. We showed that organic acids, particularly citric acid, can effectively precipitate lignin with yields comparable to the sulfuric acid method (47-60 g/dm³ vs. 50 g/dm³). Simultaneously, this method produces lignin with higher purity (regarding sulfur content) and an increased content of carboxyl groups. This latter aspect is of particular interest due to the enhanced potential of lignin's adsorption functions towards metal ions. AAS analysis confirmed that lignin precipitated with citric acid showed better adsorption efficiency towards heavy metals compared to lignin precipitated with sulfuric acid, especially for Cu²⁺ ions (80% vs. 20%) and Cr³⁺ ions (46% vs. 2%). This enhanced adsorption efficiency of the isolated lignins, combined with the environmental benefits of using organic acids, opens a promising perspective for their application in water treatment and environmental remediation. Furthermore, the presented research on the valorization and reuse of paper industry by-products fully aligns with the fundamental principles of the Circular Economy.