Resin-Mediated pH Control of Metal-Loaded Ligand Exchangers for Selective Nitrogen Recovery from Wastewaters

Highly selective separation materials that recover total ammonia nitrogen (i.e., ammonia plus ammonium, or TAN) from wastewaters as a pure product can supplement energy-intensive ammonia production and incentivize pollution mitigation. We recently demonstrated that commercial acrylate cation exchange polymer resins loaded with transition metal cations, or metal-loaded ligand exchangers, can recover TAN from wastewater with high selectivity (TAN/K⁺ equilibrium selectivity of 10.1) via metal-ammine bond formation. However, the TAN adsorption efficiency required further improvement (35%), and the optimal concentration and pH ranges were limited by both low ammonia fractions and an insufficiently strong resin carboxylate-metal bond that caused metal elution. To overcome these deficiencies, we used a zinc-acrylate ligand exchange resin and a tertiary amine acrylic weak base resin (pH buffer resin) together to achieve resin-mediated pH control for optimal adsorption conditions. The high buffer capacity around pH 9 facilitated gains in the adsorbed TAN per ligand resin mass that enhanced the TAN adsorption efficiency to greater than 90%, and constrained zinc elution (below 0.01% up to 1 M TAN) because of decreased ammonia competition for zinc-carboxylate bonds. During TAN recovery, resin-mediated pH buffering facilitated recovery of greater than 99% of adsorbed TAN with 0.2% zinc elution, holding the pH low enough to favor ammonium but high enough to prevent carboxylate protonation. For selective ion separation, solid phase buffers outperform aqueous buffers because the initial solution pH, the buffering capacity, and the ion purity can be independently controlled. Finally, because preserving the resin-zinc bond is crucial to sustained ligand exchange performance, the properties of an ideal ligand resin functional group were investigated to improve the properties beyond those of carboxylate. Ultimately, ligand exchange adsorbents combined with solid pH buffers can advance the selective recovery of nitrogen and potentially other solutes from wastewaters.