RESUMO
The development of an efficient adsorbent is required in tertiary wastewater treatment stages to reduce the phosphate-phosphorous content within regulatory levels (1 mg L-1 total phosphorous). In this study, a natural muscovite was used for the preparation of muscovite/zeolite composites and the incorporation of Fe3+/Mn2+ (oxy)hydroxide nanoparticles for the recovery of phosphate from synthetic wastewater. The raw muscovite MC and the obtained muscovite/sodalite composite LMC were used in the powder form for the phosphate adsorption in batch mode. A muscovite/analcime composite was obtained in the pellets PLMCT3 and monolith SLMCT2 forms for the evaluation in fixed-bed mode for continuous operation. The effect of pH, equilibrium and kinetic parameters on phosphate adsorption and its further reuse in sorption-desorption cycles were determined. The characterization of the adsorbents determined the Fe3+ and Mn2+ incorporation into the muscovite/zeolite composite's structure followed the occupancy of the extra-framework octahedral and in the framework tetrahedral sites, precipitation and inner sphere complexation. The adsorbents used in this study (MC, LMC, PLMCT3 and SLMCT2) were effective for the phosphate recovery without pH adjustment requirements for real treated wastewater. Physical (e.g., electrostatic attraction) and chemical (complexation reactions) adsorption occurred between the protonated Fe3+/Mn2+ (oxy)hydroxy groups and phosphate anions. Higher ratios of adsorption capacities were obtained by powder materials (MC and LMC) than the pellets and monoliths forms (PLMCT3 and SLMCT2). The equilibrium adsorption of phosphate was reached within 30 min for powder forms (MC and LMC) and 150 min for pellets and monoliths forms (PLMCT3 and SLMCT2); because the phosphate adsorption was governed by the diffusion through the internal pores. The adsorbents used in this study can be applied for phosphate recovery from wastewater treatment plants in batch or fixed-bed mode with limited reusability. However, they have the edge of environmentally friendly final disposal being promissory materials for soil amendment applications.
RESUMO
A parent Mg-Al-LDH was upgraded in its adsorption properties due to the incorporation of tri-metal species oxy(hydroxide) nanoparticles obtaining Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite for the phosphate recovery from simulated urban treated wastewater. The physicochemical properties of the synthesized Mn2+/Zn2+/Fe3+/Mg-Al-LDH make promising for real application without being environmentally harmful. The performance of Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite was evaluated through batch adsorption assays. The support of iron, manganese, and zinc (oxy)hydroxide nanoparticles onto the parent Mg-Al-LDH structure was performed by precipitation, isomorphic substitution, and complexation reactions. The main improvement of the Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite was the highest phosphate adsorption capacity (82.3 mgâg-1) in comparison to the parent Mg-Al-LDH (65.3 mgâg-1), in a broad range of concentrations and the effective phosphate adsorption at neutral pH (7.5) near to the real wastewater effluents conditions in comparison to the conventional limitations of other adsorbents. The effectiveness of Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite was higher than the conventional metal LDHs materials synthesized in a single co-precipitation step. The phosphate adsorption onto Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite was described to be governed by both physical and chemical interactions. The support of Mn2+/Zn2+/Fe3+ oxy(hydroxide) nanoparticles over the parent Mg-Al-LDH was a determinant for the improvement of the phosphate adsorption that was governed by complexation, hydrogen bonding, precipitation, and anion exchange. The intra-particular diffusion also described well the phosphate adsorption onto the Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite. Three specific stages of adsorption were determined during the phosphate immobilization with an initial fast rate, followed by the diffusion through the internal pores and the final equilibrium stage, reaching 80% of removal and the equilibrium within 1 h. The Mn2+/Zn2+/Fe3+/Mg-Al-LDH was strongly selective towards phosphate adsorption in presence of competing ions reducing the adsorption capacity at 20%. The Mn2+/Zn2+/Fe3+/Mg-Al-LDH has limited reusability, only 51% of the adsorbed phosphate could be recovered in the second cycle of the adsorption-desorption process. Around 14% of phosphate was loosely-bond to Mn2+/Zn2+/Fe3+/Mg-Al-LDH which brings the opportunity to be a new source of phosphorus. The use of eluted concentrates and the final disposal of the exhausted adsorbent for soil amendment applications can be an integral nutrient system (P, Mn, Zn, Fe) for agriculture purposes.
RESUMO
Hydrothermally synthesized Linde type A (LTA) and faujasite X (FAU-X) zeolites are low-cost and environmentally benign inorganic carriers for environmental applications. In this study, (oxy)hydroxides were incorporated onto LTA and FAU-X zeolites to promote the phosphate adsorption. The performance of LTA-Fe and FAU-X-Fe was evaluated through batch adsorption assays. A complete evaluation was performed to recover phosphate from synthetic wastewater. The effect of pH, concentration, equilibrium, and kinetic parameters on phosphate adsorption and its further reuse in sorption-desorption cycles were evaluated. LTA-Fe and FAU-X-Fe are effective for adsorption of phosphate at neutral (e.g., pH 7.0 ± 0.2) and in a broad range of phosphate concentrations. Higher ratios of adsorption capacities were obtained by synthetic zeolites enriched with iron in comparison to their parent forms. The phosphate adsorption occurred through hydrogen bonding and complexation reactions between protonated iron hydroxyl groups and phosphate anions. The phosphate monolayer adsorption was followed by diffusion through the internal pores and 80% of the equilibrium adsorption was reached within 50 min. The LTA-Fe and FAU-X-Fe can be used for phosphate recovery from wastewater treatment plants. The use of LTA-Fe and FAU-X-Fe in a tertiary wastewater treatment stage could allow to reduce the phosphate-phosphorous content, reaching the regulatory levels (equal 1 mg L-1 total phosphorous). The phosphate adsorption using LTA-Fe and FAU-X-Fe does not require pH adjustment, and it is endothermic. The reusability of both iron zeolites is limited, and they can be finally disposed for soil amendment applications.