Metal-Based Ionic Liquids in Oxidative Desulfurization: A Critical Review

Ionic liquids (ILs) as novel functional desulfurization materials have attracted increasing attentions. Metal-based ionic liquids (MILs) are classified into three types of metal chloride ILs, metal oxide ILs, and metal complex ILs based on the definition and basic structure of MILs in this critical review. On the basis of the properties of ILs such as structure designability, super dissolution performance, good thermal and chemical stability, nonflammability, and wide electrochemical window, MILs exhibit unique advantages on hydrophobicity, oxidation performance, and Brönsted-Lewis acidity. Therefore, MILs possess both the absorption and oxidation centers for the intramolecular adsorption and oxidation to improve the oxidative desulfurization (ODS) process. During the novel nonaqueous wet oxidative desulfurization process (Nasil), H₂S can be oxidized into elemental sulfur with hydrophobic MILs, which can be regenerated by oxygen for recycle, to solve the problems of low sulfur capacity, low sulfur quality, and severe secondary pollution in the aqueous Lo-Cat wet oxidative desulfurization process. Another outstanding feature of MILs in ODS is biomimetic catalysis, which has the function of activating molecular oxygen and improving the oxidation performance. Metal oxide ILs and metal complex ILs are used in combination with hydrogen peroxide or oxygen with the existing water to generate a Fenton-like reaction to convert hydrophobic organic sulfur or SO₂ into hydrophilic sulfoxide/sulfone or sulfur acid, respectively. However, the corrosion of Cl^- to the equipment and emulsification phenomenon in the extraction process of sulfoxide/sulfone separation still need further study. Furthermore, the promising strategies to construct highly efficient and green desulfurization processes for large-scale applications are provided.