Reusable and inductively regenerable magnetic activated carbon for removal of organic micropollutants from secondary wastewater effluents.

This work introduces a new sustainable alternative of powdered activated carbon (PAC) - magnetically harvestable and reusable after regeneration via inductive heating - for the adsorptive removal of organic micropollutants (OMP) from secondary wastewater effluents. For this purpose, two commercial PACs - lignite "L" (1187 m2/g) and coconut "C"-based (1524 m2/g) - were modified with magnetic iron oxide following two different synthesis approaches: infiltration ("infiltr") and surface deposition ("depos") route. The resulting magnetic powdered activated carbons (mPAC) and their precursor PACs were fully characterized before application. The iron oxide content of the modified "L" and "C" samples was ∼30 % and ∼20 %, respectively. Iron oxide gives the PAC beneficial magnetic properties for easy magnetic separation and simultaneously acts as an inductively heatable agent for the carbon regeneration. The infiltrated samples displayed better inductive heating performance and regeneration than their deposited counterparts. Tests with real wastewater showed fast adsorption kinetics of the organic load following the pseudo-second-order kinetic model. Adsorption isotherms were compliant with the Freundlich isotherm model. Sample "L-infiltr" had the best overall adsorption performance throughout 5 reuse cycles when intermediately inductively regenerated (<3 % drop in organics removal per cycle with intermediate regeneration vs. ∼10 % drop per cycle without regeneration). The treated supernatant was additionally tested for 31 representative organic micropollutants and their transformation products (pharmaceuticals, personal care products, industrial chemicals, etc.), where 26 OMPs had consistently high removal (>85 %) throughout 5 cycles with intermediate regeneration and for 28 OMPs the total adsorption efficiency dropped by <5 % after 5 cycles.

Sorption of recalcitrant phosphonates in reverse osmosis concentrates and wastewater effluents - influence of metal ions.

Magnetic microparticles functionalized with tailored ZnFeZr oxyhydroxide adsorbent were used for the reversible sorption of orthophosphate and recalcitrant organo-phosphonates from wastewater. The loaded particles were harvested magnetically from water, regenerated in an alkaline solution and reused numerous times. The applicability of the technology to treat brackish water reverse osmosis concentrates was tested under controlled synthetic conditions by investigating the influence of typical metals (Ca2+, Pb2+, Cu2+) on the removal of common phosphonates (HEDP, NTMP, EDTMP), and vice versa. When present at equimolar concentrations, metal cations enhanced the adsorption of phosphonates and were co-adsorbed at pH 4.0-4.5 (with removals of 83-93% for Pb2+ and 53-73% for Cu2+), likely through ternary complex formation. In the absence of metals, at pH > pHPZC ∼ 7 (the material point of zero charge), a drop in adsorption efficiency was observed for orthophosphate and all phosphonates. Thus, at pH 7, an increased adsorbent dose (>0.1 g/L) was necessary to remove 1 mg/L NTMP-P in 30 min. The reusability and effluent polishing potential of the ZnFeZr particles was demonstrated in a pilot test with municipal wastewater throughout 55 adsorption/desorption cycles without any drop in performance. Consistent removal of the non-reactive phosphorus species to ultra-low concentrations (<0.05 mg/L Ptot) and complete orthophosphate elimination (<0.005 mg/L PO4-P) was maintained under optimal conditions.

Phosphorus recovery from sewage sludge - phosphorus leaching behavior from aluminum-containing tertiary and anaerobically digested sludge.

Systematic investigations of the acidic dissolution of phosphorus (P), aluminum (Al), iron (Fe), and calcium (Ca) from Al-containing tertiary sludge were carried out in this work. The results were compared with the dissolution behavior of Al-containing anaerobically digested sludge to evaluate the P recovery potential in the form of struvite from tertiary sludge versus anaerobically digested sludge. Additional investigations of synthetically produced Al sludge served as a comparison for the dissolution behavior of P and Al without the influence of other contaminants (metals, biomass). In addition, the acid consumption was analyzed as a function of the target pH during the dissolution. The dissolution efficiency of ortho-phosphate in tertiary and anaerobically digested sludge after acid treatment at pH 2 was ∼90%. The dissolution efficiency of Al and Ca in tertiary sludge was also ∼90% at pH 2, while the release efficiency of Al and Ca in anaerobically digested sludge was lower, ∼70% at pH 2. In tertiary sludge, about 75% of Fe was found dissolved at pH 2, whereas in anaerobically digested sludge this value was higher, ∼90%. Based on the experimental data, it can be concluded that significant dissolution of phosphorus from Al-containing tertiary sludge can take place at pH < 3. The highest sulfuric acid consumption for P dissolution was observed in the case of tertiary sludge at pH 2.

Removal of phosphonates from synthetic and industrial wastewater with reusable magnetic adsorbent particles.

This work proposes a technology for phosphonate removal from wastewater using magnetically separable microparticles modified with a tailored ZnFeZr-oxyhydroxide adsorbent material which proved to be highly efficient, reaching a maximum loading of ∼20 mg nitrilotrimethylphosphonic acid-P/g (215 µmol NTMP/g) at room temperature, pH 6 and 30 min contact time. The adsorption process at pH < 7 was fast, following the pseudo-second-order kinetics model. Furthermore, NTMP adsorption onto ZnFeZr-oxyhydroxide proved to be endothermic. At pH > pHpzc ≈7 (point of zero charge of the material) a drop in adsorption efficiency was observed for phosphate and for five different investigated phosphonates. Adsorption of NTMP could not be detected at pH > 8, however, the presence of more than 0.5 mM CaII improved significantly the adsorption efficiency. Successful reusability of the engineered particles was demonstrated throughout 30 loading cycles by changing the operational conditions (dose, pH) to optimize the performance. At optimal conditions, complete phosphonate removal was observed even after 30 cycles of particles' reuse in a synthetic NTMP-solution and DTPMP-rich membrane concentrate. In each cycle, phosphorus was desorbed and concentrated in a 2 M NaOH. Industrial phosphonate-containing wastewaters rich in calcium, e.g. membrane concentrates, proved to be especially suitable for treatment with the particles.

Pilot-scale removal and recovery of dissolved phosphate from secondary wastewater effluents with reusable ZnFeZr adsorbent @ Fe3O4/SiO2 particles with magnetic harvesting.

Advanced nanocomposite magnetic particles functionalized with ZnFeZr-adsorbent are developed, characterized and tested for the removal and recovery of phosphate directly from spiked secondary wastewater effluent (∼10 mg/L PO4-P). The phosphate loaded particles can be extracted from the liquid phase via magnetic separation, regenerated in a NaOH solution where phosphate desorption takes place, and reused in numerous cycles. Laboratory experiments demonstrate their reusability and stability in 60 consecutive adsorption/desorption runs where under optimal conditions > 90% total P-recovery efficiency is reached. In addition, pilot tests are performed to verify the proof-of-concept by upscaling the technology and maintain high efficiency of phosphate removal and recovery after treating 1.5 m3 wastewater in 20 cycles. Effluent concentrations <0.05 mg/L PO4-P can be achieved in the treated wastewater. The reclaimed desorption solution is concentrated with phosphate ions through its repetitive application, attaining up to 38-times enrichment (∼380 mg/L PO4-P) compared to the initial concentration in wastewater. The P-rich eluate is used as a source for subsequent precipitation of a solid fertilizer product such as struvite.

Phosphate recovery from wastewater using engineered superparamagnetic particles modified with layered double hydroxide ion exchangers.

An innovative nanocomposite material is proposed for phosphate recovery from wastewater using magnetic assistance. Superparamagnetic microparticles modified with layered double hydroxide (LDH) ion exchangers of various compositions act as phosphate adsorbers. Magnetic separation and chemical regeneration of the particles allows their reuse, leading to the successful recovery of phosphate. Based upon the preliminary screening of different LDH ion exchanger modifications for phosphate selectivity and uptake capacity, MgFe-Zr LDH coated magnetic particles were chosen for further characterization and application. The adsorption kinetics of phosphate from municipal wastewater was studied in dependence with particle concentration, contact time and pH. Adsorption isotherms were then determined for the selected particle system. Recovery of phosphate and regeneration of the particles was examined via testing a variety of desorption solutions. Reusability of the particles was demonstrated for 15 adsorption/desorption cycles. Adsorption in the range of 75-97% was achieved in each cycle after 1 h contact time. Phosphate recovery and enrichment was possible through repetitive application of the desorption solution. Finally, a pilot scale experiment was carried out by treating 125 L of wastewater with the particles in five subsequent 25 L batches. Solid-liquid separation on this scale was carried out with a high-gradient magnetic filter (HGMF).