Fixed-bed adsorption of methylene blue using granular NaX zeolite/attapulgite composite: efficiency, mechanism and reusability of saturated G-NaX/A

Abstract

A novel granular NaX zeolite/attapulgite (G-NaX/A) composite was developed to address the challenges of high pressure drop in fixed beds with powder synthetic zeolite and low adsorption capacity of natural zeolite. The synthesized G-NaX/A retains the micropores of NaX and the mesoporous of attapulgite. The BET specific surface area reached 481.17 m2/g, and the total pore volume was 0.3549 cm3/g. The G-NaX/A maximum methylene blue (MB) adsorption capacity was 1.56 times that of commercial granular activated carbon (7.41 mg/g). The breakthrough time and adsorption capacity improved with lower influent flow rate and MB concentration and higher pH. Under optimal conditions (flow rate: 150 mL/min, MB concentration: 25 mg/L, pH = 8), it achieved a maximum adsorption capacity of 11.51 mg/g and a breakthrough time of 2.54 h. The adsorption behavior of G-NaX/A was well-fitted by the Yoon–Nelson and Thomas models at different operating conditions. The mechanism studies revealed that MB (cation: C16H18SN3+) removal by G-NaX/A occurred through electrostatic attraction, ion exchange with Na+/Mg2+, surface coordination with ≡Al/SiOH, and surface physical adsorption. The regeneration studies confirmed the reusability potential of G-NaX/A by calcining at 500 °C for 2 h, and significantly improved adsorption capacity reaching about 14.39 mg/g, 16.31 mg/g and 14.07 mg/g across the three adsorption-regeneration cycles respectively. The findings support G-NaX/A technical feasibility, high adsorption capacity and potential for further scaling in fixed bed adsorption studies.