Thermally Modified Palygorskite Usage as Adsorbent in Fixed-Bed Reactor for High Concentration NH4+-N Removal and Further Application as N-Fertilizer in Hydroponic Cultivation.

Palygorskite sample (Pal) underwent thermal treatment at 400 °C (T-Pal) to be used as adsorbent for the removal of 200 mg NH4+-N/L from artificial solution. After thermal treatment, the sample was characterized via X-ray diffraction (XRD) and scanning electron microscopy (SEM). For NH4+-N removal, T-Pal was added as a bed matrix in fixed-bed reactor experiments and the effect of flow rate was determined. It was indicated that with the flow rate increase from 10 mL/min to 50 mL/min, fewer liters of the solution were purified, rendering a longer residual time of interactions, which is optimal for NH4+-N removal from T-Pal. The maximum removed amount was calculated at 978 mg NH4+-N (qtotal), suggesting T-Pal is a promising ammonium adsorbent. The data of kinetic experiments were applied to Clark, Yoon-Nelson, and Thomas kinetic models, with Clark having the best fit, highlighting a heterogenous adsorption. At the end of kinetic experiments, T-Pal applied in hydroponic cultivations and presented a sufficient release rate, which was found utilizable for saturated T-Pal usage as N fertilizer that satisfactory results were deemed concerning lettuces characteristics and growth.

Using raw and thermally modified fibrous clay minerals as low concentration NH4+-N adsorbents.

Raw and modified fibrous clay minerals palygorskite (Pal) and sepiolite (Sep) were tested for their ability to remove ammonium from ammonium polluted water. Palygorskite and sepiolite underwent thermal treatment at 400°C (T-Pal and T-Sep respectively). Raw and thermally treated samples were characterized using XRD, SEM, BET, FTIR, TGA, zeta potential, and XRF. The techniques verified the effect of thermal treatment on sample structures and the enhancement of negative charge. Both raw and thermally activated materials were applied in batch kinetic experiments, and found to be efficient adsorbents in their raw forms, since Pal and Sep achieved 60 and 80% NH4+-N removal respectively within 20 min of contact for initial NH4+-N concentration of 4 mg/L. Similar removal rates were gained for other concentrations representative of contaminated aquifers that were examined, ranging from 1 to 8 mg/L. Results for the modified T-Pal and T-Sep minerals showed up to 20% higher removal rate. Saturation tests indicated the positive effect of thermal treatment on the minerals since T-Pal and T-Sep removal efficiency reached 85% and remained stable for 24 h. However, competitive ions in real water samples can influence the NH4+-N removal efficiency of the examined samples. At almost all the examined samples, the nonlinear Freundlich isotherm and linear pseudo-second kinetic models showed better fitted all examined samples thus indicating heterogeneous chemisorption.

Raw and modified palygorskite in water treatment applications for low-concentration ammonium removal.

Raw palygorskite (Pal) samples went under acid (H-Pal), NaCl (Na-Pal), and CaCl2 treatment (Ca-Pal) in order to be examined as ammonium (NH4 + ) sorbents from aqueous solutions. The samples were characterized by XRD and FT-IR techniques to examine potential structural differences after modifications, and batch kinetic experiment series were applied to determine the optimal conditions for NH4 + removal. According to thermodynamic analysis, the removal reaction for sodium- and calcium-treated samples was endothermic (ΔΗ0  > 0, 1.65 kJ/mol and 24.66 kJ/mol, respectively), in contrast with the exothermic reactions of raw and acidic-treated palygorskite samples (ΔΗ0  < 0, -37.18 kJ/mol and -27.56 kJ/mol respectively). Moreover, each sample presented a different order of sorbed ions preference, whereas the strong affinity for Ca2+ sorption was common in all cases since the NH4 + removal inhibited. Nevertheless, a similar pattern was followed for raw and modified samples at isotherm study, rendering the linear form of Freundlich isotherm to express better the NH4 + sorption on palygorskite sample, indicating that it is a heterogeneous procedure. In all cases, the NH4 + maximum uptake was within 15 min using 8 g/L of each sorbent, especially for the Na-Pal sample, which could reach almost 100% removal of low concentration NH4 + . PRACTITIONER POINTS: Modified palygorskite samples were tested for NH4 + removal from aqueous solutions. NaCl-treated palygorskite had the higher removal efficiency, which could reach almost 100% removal of low concentration NH4 + . NH4 + maximum uptake was within 15 minutes using 8 g/L of each sorbent. NH4 + adsorption was an endothermic reaction for NaCl- and CaCl2 -treated palygorskite sorbents. NH4 + adsorption was an exothermic reaction for raw and acid-treated palygorskite sorbents.