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.

Electro-assisted regeneration of pH-sensitive ion exchangers for sustainable phosphate removal and recovery.

Removal and recovery of phosphate from wastewater can minimize deleterious environmental impacts and supplement fertilizer supply. Hybrid anion exchangers (HAIX, with doped ferric oxide nanoparticles (FeOnp)) can remove phosphate from complex wastewaters and recover concentrated phosphate solutions. In this study, we integrate HAIX with a weak acid cation exchanger (WAC) to enrich phosphate and calcium in mild regenerants and precipitate both elements for recovery. We demonstrated an electro-assisted regeneration approach to avoid strong acid and base input. Based on demonstrated pH sensitivities of both materials, electrochemically produced mild electrolytes (pH 3 and pH 11), which are 100-1000 times less concentrated than typical regenerants, preserved 80% WAC and 50% HAIX capacities over five batch adsorption-regeneration cycles. FeOnp in HAIX facilitated regeneration due to pH sensitivity and their likely distribution on the resin particle surface, which reduced intraparticle diffusion path length. In column tests, repeatable phosphate removal (> 95%) from synthetic wastewater (3 mg P/L) was achieved with 20 kWh/kg P specific energy consumption. After removal, a similar 50% HAIX regeneration efficiency as batch experiments was achieved. In spent regenerant, more than 95% phosphorus was recovered as hydroxyapatite. This novel approach enhances ion exchange by minimizing chemical inputs.

Quantitative Evaluation of an Integrated System for Valorization of Wastewater Algae as Bio-oil, Fuel Gas, and Fertilizer Products.

Algal systems have emerged as a promising strategy for simultaneous treatment and valorization of wastewater. However, further advancement and real-world implementation are hindered by the limited knowledge on the full energetic and nutrient product potentials of such systems and the corresponding value of these products. In this work, an aqueous-based system for the conversion of wastewater-derived algae and upgrading of crude products was designed and demonstrated. Bio-oil, fuel gas, and fertilizer products were generated from algal biomass harvested from a municipal wastewater treatment facility. Experiments showed that 68% of chemical energy contained in the algal biomass could be recovered with 44% in upgraded bio-oil and 23% in fuel gas (calculated as higher heating values), and 44% and 91% of nitrogen and phosphorus element contents in the original feedstock could be recovered as fertilizer products (ammonium sulfate and struvite), respectively. For 1,000 kg of such dry algal biomass, these products had an estimated total value of $427 (in 2014 U.S. dollars). For the first time, experiment-based energy and nutrient recovery potentials of wastewater-derived algae were presented in an integrated manner. Findings also revealed critical research needs and suggested strategies to further improve resource recovery and waste valorization in these systems.