Cationic Lignin Polymers as Flocculant for Municipal Wastewater

Abstract

The radical polymerization of acid-washed and unwashed softwood kraft lignin with [2-(methacryloyloxy) ethyl] trimethylammonium chloride (METAC) was attempted to investigate the production of lignin-based flocculants for simulated wastewater. The incorporation of METAC onto lignin resulted in a cationic charge density (2.3-3.3 meq/g), increased water solubility (89-96% in neutral pH), and increased molecular weight (70,000-210,000 g/mol) of lignin. The lignin-METAC polymers generated from acid-washed lignin had higher molecular weights than those generated from unwashed lignin. The lignin-METAC polymers showed lower resistance to thermal decomposition than unmodified lignin due to the inclusion of PolyMETAC. The unmodified acid-washed lignin samples did not significantly affect the COD of the wastewater, while the unmodified unwashed lignin samples contributed to the COD, implying that unmodified lignin was not suitable for wastewater treatment. The flocculation of wastewater with lignin-METAC led to the chemical oxygen demand (COD) reduction of 17-23% and total organic carbon (TOC) drop of 51-60%. The lignin-METAC polymer with the highest molecular weight (produced from acid-washed lignin) reached the highest COD removal, while lignin-METAC polymer with the highest charge density (produced from unwashed lignin) reached the highest TOC removal. Focused beam reflectance measurement (FBRM) studies revealed that the lignin-METAC polymer produced from acid-washed lignin with a high molecular weight generated larger and more flocs in wastewater than the lignin-METAC polymer produced from unwashed lignin. The comparison of theoretical and experimental dosages required for neutralizing the charges of wastewater demonstrated that charge neutralization was the main flocculation mechanism, although a bridging mechanism was also involved for component removals from wastewater. The use of 1 mg/L of alum along with 65 mg/L lignin-METAC in a dual coagulation-flocculation system led to higher average phosphorous (42%) and COD (44%) removals than the singular flocculation system only using 65 mg/L of lignin-METAC (with phosphorous removals of 3.4% and COD removals of 18.7%). However, lignin-METAC flocculant slightly increased the ammonia-nitrogen content in both singular flocculation and dual coagulation-flocculation systems due to the residual ammonia content of lignin-METAC. The coagulation-flocculation system determined that the use of lignin-METAC (65 mg/L) could reduce the alum dosage significantly while maintaining a similar organic content reduction of 44% for wastewater.

Keywords: coagulation; flocculation; lignin polymerization; municipal wastewater.

Figure 1

³¹PNMR spectrum of AWL1 with aliphatic (δ 145.4–150.0 ppm), C₅ substituted (δ 140.0–144.5 ppm), Sinapyl (δ ≈142.7 ppm), conideryl (δ 139.0–140.2 ppm), p-coumaryl (δ ≈137.8 ppm), and carbocyclic (δ 133.6–136.0 ppm).

Figure 2

COD of municipal wastewater as a function of unmodified lignin dosage.

Figure 3

(a) COD and (b) zeta potential as a function of lignin-METAC dosage for municipal wastewater treatment.

Figure 4

Number of counts as a function of the chord length of flocs formed after the addition of 65 mg/L lignin–METAC polymer in synthetic municipal wastewater.