Chemical interactions between metal particles (Ag or Ni) dispersed in a low-cost MCM-41M produced from beach sand amorphous silica and sulfur compounds were evaluated in the deep adsorptive desulfurization process of real diesel fuel. N2 adsorption-desorption isotherms, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy coupled to energy-dispersive X-ray spectroscopy (STEM-EDX) were used for characterizing the adsorbents. HRTEM and XPS confirmed the high dispersion of Ag nanoparticles on the MCM-41 surface, and its chemical interaction with support and sulfur compounds by diverse mechanisms such as π-complexation and oxidation. Thermodynamic tests indicated that the adsorption of sulfur compounds over Ag(I)/MCM-41M is an endothermic process under the studied conditions. The magnitude of ΔH° (42.1 kJ/mol) indicates that chemisorptive mechanisms govern the sulfur removal. The best fit of kinetic and equilibrium data to pseudo-second order (R2 > 0.99) and Langmuir models (R2 > 0.98), respectively, along with the results for intraparticle diffusion and Boyd’s film-diffusion kinetic models, suggest that the chemisorptive interaction between organosulfur compounds and Ag nanosites controls sulfur adsorption, as seen in the XPS results. Its adsorption capacity (qm = 31.25 mgS/g) was 10 times higher than that obtained for pure MCM-41M and double the qm for the Ag(I)/MCM-41C adsorbent from commercial silica. Saturated adsorbents presented a satisfactory regeneration rate after a total of five sulfur adsorption cycles.
SBA-15 materials as-synthesized and impregnated with Ag nanoparticles were applied to perform adsorptive desulfurization of real diesel fuel. High-angle annular dark-field scanning transmission electron microscopy and field-emission scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (HAADF-STEM-EDX and FESEM-EDX) and X-ray photoelectron spectroscopy (XPS) results confirmed that there is uniform distribution of Ag nanodomains on the surface and in the channels of a 2AgSBA-15 (2% Ag) sample. The interaction between sulfur compounds and adsorbent mainly occurred via π-complexation mechanisms, as observed via XPS and equilibrium data. The kinetic results for 2AgSBA-15 were better fitted to the pseudo-second-order model (R2 > 0.9999), indicating that the determining step of the adsorptive process is chemisorption, whereas the equilibrium results were better fitted to the Langmuir model (R2 > 0.9994), thus indicating that the adsorption occurs on the adsorbent surface monolayer with significant adsorption capacity (qm = 20.30 mgS/g), approximately two times greater than that observed for pure SBA-15. The mean desulfurization reached by the adsorbents was up to 86.8% for six recycling steps.
25 April 2022 in Korean Journal of Chemical Engineering
Pharmaceutical contamination of water sources has become a critical environmental challenge. Bentonite (BN), a natural clay mineral, has gained attention due to its high surface area, cation exchange capacity, and cost-effectiveness, making it a promising adsorbent for removing contaminants. This study explores the potential of BN and its acid-treated form (BA1) as effective adsorbents for the removal of tetracycline hydrochloride (TC) from aqueous solutions. Comprehensive characterization was performed using analytical techniques, including XRF, XRD, SEM/TEM, XPS, TG/DTG, and CO2 and N2 adsorption–desorption isotherms. The results indicate that BA1 is a mesoporous material with a surface area exceeding 165 m2·g−1. The adsorption process was fitted to a pseudo-second-order kinetic model. BA1 achieved a maximum adsorption capacity of 40.98 mg·g−1 and removal efficiency of up to 99% within only 30 min at an optimal pH of 5. Equilibrium isotherm calculations for BA1 show the best fit for the Freundlich model R2 > 0.9923, indicating a favorable adsorption process. The material was reused over seven consecutive cycles to evaluate the regeneration capacity of the clay mineral materials. BN stands out for its effectiveness, cost-effectiveness, and environmental sustainability as a promising material for water treatment applications.