Role of alkali and alkaline-earth doped in zeolite A-derived from industrial waste toward direct ethanol dehydrogenation to acetaldehyde

Abstract

In this study, a sustainable catalytic route for converting ethanol into value-added acetaldehyde was developed using alkali- and alkaline earth-modified zeolite A synthesized from sugarcane bagasse ash (SCBA). Zeolite A was first prepared via alkaline fusion followed by hydrothermal crystallization and subsequently doped with 1 wt% K^+ or Ca^2+ using incipient wetness impregnation. Comprehensive physicochemical characterization (X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), Fourier transform infrared spectroscopy (FTIR), nitrogen physisorption (N_2 physisorption), ammonia temperature-programmed desorption (NH_3-TPD), and carbon dioxide temperature-programmed desorption (CO_2-TPD)) confirmed the formation of a highly crystalline LTA framework with tunable acid-base properties upon cation incorporation. Catalytic evaluation demonstrated that ethanol dehydrogenation strongly depends on the balance of surface acid-base sites. The parent and Ca-modified zeolite A exhibited moderate acetaldehyde selectivity (11.2% and 21.2%, respectively), likely due to competing dehydration reactions. In contrast, K-modified zeolite A achieved higher acetaldehyde selectivity (51.8%) at 35.2% ethanol conversion, attributed to enhanced surface basicity and suppressed acidity. Mechanistic analysis suggests that K^+ and Ca^2+ promote ethanol dehydrogenation by facilitating ethoxide formation and β-hydrogen elimination on basic lattice oxygen sites. These findings demonstrate a cost-effective, noble-metal-free catalytic strategy and highlight the potential of SCBA-derived zeolite A as a sustainable platform for green ethanol upgrading.