Oxidative desulfurization of model diesel via dual activation by a protic ionic liquid

Highlights: • A protic ionic liquid, [Hnmp]HCOO, was used as in ODS. • The mechanism of ODS was involved in dual activation by the PIL. • The [Hnmp]HCOO exhibited high catalytic activity in ODS. • The amounts of PILs and oxidant dosage play vital roles in desulfurization system. • This system can be recycled five times with an unnoticeable decrease in activity. - Abstract: A novel and green carboxylate-anion-based protic ionic liquid (PIL), [Hnmp]HCOO, was prepared through a simple and atom economic neutralization reaction between N-methyl-2-pyrrolidonium (NMP) and formic acids. Both FT-IR spectra and ¹H NMR confirmed its simple salt structure. [Hnmp]HCOO exhibited so high catalytic activity that the dibenzothiophene (DBT) removal reached 99% at 50 °C in 3 h under conditions of V_PIL/V_{model oil} = 1:10 and H₂O₂/DBT (O/S, molar ratio) = 5. The catalytic oxidation reactivity of S-compounds was found to be in the order of DBT > 4,6-dimethyldibenzothiophene (4,6-DMDBT) > benzothiophene (BT). The investigation on mechanism showed that oxidative desulfurization was realized through dual activation of PIL. Moreover, [Hnmp]HCOO can be recycled for five times with an unnoticeable decrease in desulfurization activity