The adsorptive extraction of oxidized sulfur-containing compounds from fuels by using molecularly imprinted chitosan materials

摘要

An innovative approach for desulfurisation of fuels is proposed. It relies on the formation of recognition sites, complementary to oxidized sulfur-containing compounds, on cross-linked chitosan microspheres and electrospun chitosan nanofibers using the molecularly imprinted polymer technique. Benzothio-phene sulfone (BTO_2), dibenzothiophene sulfone (DBTO_2) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO_2) were used as templates for the preparation of molecularly imprinted polymers (MIPs). The possible molecular interactions between imprinted chitosan adsorbent and oxidized sulfur-containing compounds were investigated by molecular modeling using density functional theory (DFT) and results indicated that interactions took place via hydrogen bonding. The molecularly imprinted polymer adsorbents (cross-linked microspheres and electrospun nanofibers) gave better selectivity for the target sulfonated compounds and the adsorption isothermal studies followed the Freundlich model. Maximum adsorption capacities of 8.5 ± 0.6 mg/g, 7.0 ± 0.5 mg/g and 6.6 ± 0.7 mg/g were observed for model BTO_2, DBTO_2 and 4,6-DMDBTO_2 respectively at 1 mL/h when imprinted nanofibers were employed, and the imprinted microspheres gave maximum adsorption capacity of 4.9 ± 0.5 mg/g, 4.2 ± 0.7 mg/g and 3.9 ± 0.6 mg/g for BTO_2, DBTO_2 and 4,6-DMDBTO_2 respectively. Application of the nanofibers to oxidized hydro-treated fuel under continuous flow adsorption system at 1 mL/h indicated that 84% of sulfur was adsorbed, with adsorption capacity of 2.2 ± 0.2 mg/g.