Dual lignin-derived polymeric system for peptone removal from simulated wastewater.

The long-term existence of peptone can breed a large number of bacteria and cause the eutrophication of municipal wastewater. Thus, removing peptone in the wastewater is a major challenge facing the current industry. This study used cationic and anionic lignin polymers, i.e., kraft lignin-[2-(methacryloyloxy)ethyl] trimethylammonium methyl sulfate (cationic lignin polymer, CLP) and kraft lignin-acrylic acid (anionic lignin polymer, ALP), as flocculants to eliminate peptone from model wastewater in the single and dual component systems. The affinity of peptone for ALP or CLP was assessed by quartz crystal microbalance with dissipation, X-ray photoelectron spectroscopy, contact angle, and vertical scan analyzer. Results illustrated that the adsorption effect of CLP for peptone was significantly superior to that of ALP owing to the stronger vital interaction between cationic polymer and peptone molecules. Based on destabilization and sedimentation analyses, introducing CLP triggered the preliminary flocculation of peptone via bridging action, as indicated by a considerable increment in the destabilization index (from 1.1 to 10.6). Moreover, peptone adsorbed more on the CLP coated surface than on the ALP coated one (14.8 vs 5.4 mg/m2), while ALP facilitated its further adsorption in the dual polymer system. This is because CLP adsorbed a part of peptone molecules on its surface. Then, ALP entrapped the unattached peptone onto the CLP coated surface through electrostatic interaction. Compared with the single polymer system, mixing ALP and CLP subsequently into the peptone solution in the dual system generated larger size aggregates (mean diameter of 6.1 µm) and made the system destabilization (Turbiscan stability index up to 58.1), thereby yielding more flocculation and sedimentation. Finally, peptone was removed successfully from simulated wastewater with a turbidity removal efficiency of 92.5%. These findings confirmed that the dual-component system containing two lignin-derived polymers with opposite charges could be viable for treating peptone wastewater.

Dual lignin-derived polymeric systems for hazardous ion removals.

The functionalization of lignin derivatives for ion removals is a promising method to expedite their use in treating industrial wastewater. In this work, kraft lignin (KL) was polymerized with [2-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate (METAM) or acrylic acid (AA) in an acidic aqueous suspension system to produce cationic and anionic water-soluble lignin polymers with high molecular weights. Then, the interaction of soluble ions and KL-METAM and KL-AA was investigated using a Quartz crystal microbalance (QCM) and a vertical scan analyzer (VSA). The QCM, X-ray photoelectron spectroscopy (XPS) and contact angle measurement results showed that the adsorption efficiency of KL-AA was better than KL-METAM for ions due to the stronger electrostatic interaction, cationic π-interaction, and chelation between ions and KL-AA. Based on adsorption, sedimentation, and aggregate size analyses, the dual polymer systems of KL-AA/KL-METAM were more effective than KL-METAM/KL-AA in removing ions. Among Zn2+, Cu2+, and K+; Zn2+ interacted more effectively with polymers in all scenarios because it has higher reactivity for interacting with other elements. As the efficiency of ion removals was more remarkable than past reported findings, the system of KL-AA/KL-METAM may be a promising alternative for the removal of dissolved ions from solutions.

Production and Application of Triblock Hydrolysis Lignin-Based Anionic Copolymers in Aqueous Systems.

Although lignin is currently an under-utilized biopolymer, it has the potential to be valorized through different modification pathways to yield alternative products to petroleum-based ones. In this work, hydrolysis lignin (HL) was copolymerized with acrylamide (AM) and acrylic acid (AA) under acidic conditions to generate the lignin/AM polymer (HM), lignin/AA polymer (HA), and lignin/AM/AA copolymer (HAM) with different negative charge densities and molecular weights. Lignin-based polymers characterized by advanced tools, such as proton nuclear magnetic resonance (1H NMR), gel permission chromatography (GPC), and elemental analysis confirmed the successful polymerization of HL with AM, AA, or AM/AA monomers. The adsorption analysis using a quartz crystal microbalance (QCM) revealed that compared to diblock HM and HA, the triblock copolymers of HAM adsorbed more on the Al2O3 surface and generated a bulkier adsorbed layer, which is important for lignin-based coating formulation. HAM1 with a lower charge density yielded a higher surface excess density, while HAM2 with a larger R h occupied more space (153.7 Å2) at the interface of water and Al2O3. In suspension systems, because of the higher M w, R h, and adsorption affinity, the bridging performance of HAM2 was more remarkable than that of the other lignin derivatives for Al2O3 particles via forming stronger flocs (with a deflocculation parameter, T df, of 80.6 s). However, the diblock lignin-AA (HA1) polymer showed the fastest floc regrowth capability after reducing the shear forces (with a reflocculation parameter, T rf, of 62.5 s). The high thermal stability, T g, and rheological characteristics of the HAM copolymer proved that it can be an excellent material for coating formulations and flocculants for wastewater treatment systems.

Polarity of Cationic Lignin Polymers: Physicochemical Behavior in Aqueous Solutions and Suspensions.

The structure of cationic monomers can significantly impact the polarity of lignin after polymerization. Cationic hydrolysis lignin (CHL) polymers were produced by polymerizing hydrolysis lignin (HL) with [3-(methacryloylamino)propyl] trimethylammonium chloride (MAPTAC) or [2-(methacryloyloxy)ethyl] trimethyl ammonium chloride (METAC). The METAC monomer has an oxygen atom, with larger electronegativity, in its molecular structure, whereas the MAPTAC monomer contains a nitrogen atom, as well as an extra nonpolar CH2 group, facilitating investigation into the effects of the polarity of CHLs on their physicochemical performance in an aqueous system. CHL polymers are analyzed and their interactions with clay particles are determined in colloidal systems. CHLs are designed to have similar charge densities (2.1-2.2 mmol g-1) and molecular weights (55000-60000 g mol-1 ). The hydrodynamic radius (Hy) and radius of gyration, (Rg) of HL-METAC are larger than those of HL-MAPTAC, implying a more 3-dimensional structure of HL-METAC in aqueous solution. The stability ratio of kaolin particles affirms the better performance of HL-METAC in comparison to HL-MAPTAC, which reflects the better flocculation efficiency of HL-METAC. The results also reveal that salt and urea aqueous solutions affect the Hy, Rg, and configuration of CHL polymers, which alters the flocculation efficiency of HL-METAC and HL-MAPTAC polymers in kaolin suspensions.

Phenomenological Changes in Lignin Following Polymerization and Its Effects on Flocculating Clay Particles.

Cationic kraft lignin (CKL) macromolecules were produced via polymerizing kraft lignin (KL) with [2-(acryloyloxy)ethyl]trimethylammonium chloride (ATAC) or [2-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate (METAM). Despite slightly different charge densities (2.3-2.5 mmol/g) of CKL, lignin-METAM (KL-METAM) had a significantly larger molecular weight and radius of gyration. A correlation was observed between the structure of CKLs and their impacts on the surface hydrophilicity of kaolin particles. In interacting with kaolin particles, KL-METAM generated larger and stronger flocs with looser structures than did KL-ATAC. Compared to ATAC, METAM had one additional methyl substituent on its structure, which provided fundamental evidence on how a small group (i.e., a methyl group) on the structure of a cationic monomer can have a substantial influence on its polymerization with lignin and subsequently on the efficiency of the induced macromolecule as a flocculant in a kaolin suspension system.