Adsorption of dibenzothiophene sulfone using Fe3+ and Fe6+-impregnated clay adsorbents

Abstract

In this study, the adsorption of dibenzothiophene sulfone (DBTO) was investigated using clay minerals as adsorbents. Raw bentonite (BR) and raw activated clay (ACR) were impregnated with Fe3+ and Fe6+, creating bentonite-Fe3+ (BF3), bentonite-Fe6+ (BF6), activated clay-Fe3+ (ACF3), and activated clay-Fe6+ (ACF6). The surface functional groups, surface morphology, and surface area of the raw and modified adsorbents were studied through Fourier transform infrared spectroscopy, a scanning electron microscope, and Brunauer, Emmett, and Teller analysis, respectively. Batch experiments on simulated oil were done to test the effect of adsorption time (0.5–24 h), adsorption dosage (0.3–1.5 g), and adsorption temperature (30–50 °C). The results of the experiments showed the suitability of the pseudo-second order kinetic model on the clay adsorbent and sulfone system. This suggests that chemisorption is the rate-limiting step of the reaction. Equilibrium isotherms indicated the adherence of DBTO onto BR and BF3 to the Freundlich model, implying the heterogeneous adsorption of the sulfones onto the adsorbents. The systems of DBTO with BF6, ACR, ACF3, and ACF6 showed a better fit with the Dubinin-Radushkevich model. This denotes that adsorption happens through the filling of sulfones of the micropores on the adsorbent. Lastly, thermodynamic studies revealed the endothermic and non-spontaneous nature of the clay adsorbents and sulfone systems. The experiments showed that the impregnation of Fe3+ and Fe6+ lowered the desulfurization ability of the adsorbents. This could be due to the iron ions being hard acids and the sulfones being soft bases, thus showing lower compatibility than the raw counterparts of the adsorbents. Comparison with related studies showed that the prepared adsorbents, namely BF3 (5.1 mg g−1) and BF6 (6.4 mg g−1), had a higher adsorption capacity than Ni2+-loaded activated carbon (4.9 mg g−1) and activated clay (4.1 mg g−1). The study shows that BR (7.2 mg g−1) is the best-performing adsorbent, which can be set as the direction for future research. This study is a step toward the commercialization of oxidative desulfurization methods.