Kinetics and thermodynamics of organo-sulfur-compound desorption from saturated neutral activated alumina

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Desulfurization of liquid fuels mitigates the amount of noxious sulfur oxides and particulates released during fuel combustion. Existing literature on oxidative-adsorptive desulfurization technologies focus on sulfur-in-fuel removal by various materials, but very little information is presented about their desorption kinetics and thermodynamics. Herein, we report for the first time, the mechanism of sulfur desorption from neutral activated alumina saturated with dibenzothiophene sulfone. Batch experiments were conducted to examine the effects of agitation rate, desorption temperature, sulfur content, and eluent type on sulfur desorption efficiencies. Results show enhanced desorption capacities at higher agitation rate, desorption temperature, and initial sulfur content. Desorption efficiency and capacity of acetone were found to be remarkably superior to ethanol, acetone:ethanol (1:1), and acetone:isopropanol (1:1). Desorption kinetics reveal excellent fit of the nonlinear pseudo-second-order equation on desorption data, indicating chemisorption as the rate-determining step. Results of the thermodynamics study show the spontaneous (ΔG° ≤ -2.08 kJ mol-1) and endothermic (ΔH° = 32.35 kJ mol-1) nature of sulfur desorption using acetone as eluent. Maximum regeneration efficiency was attained at 93% after washing the spent adsorbent with acetone followed by oven-drying. Scanning electron microscopy, Fourier transform infrared, and X-ray diffraction spectroscopy analyses reveal the intact and undamaged structure of neutral activated alumina even after adsorbent regeneration. Overall, the present work demonstrates the viability of neutral activated alumina as an efficient and reusable adsorbent for the removal of sulfur compounds from liquid fossil fuels.