Removal of residual functionalized ionic liquids from water by ultrasound-assisted zero-valent iron/activated carbon

Numerous applications of ionic liquids (ILs) are often accompanied by the generation of aqueous wastes. Due to the high toxicity and poor biodegradability of ILs, effective chemical treatment is of great importance for their removal from aqueous solution. In this work, an ultrasound-assisted zero-valent iron/activated carbon (US-ZVI/AC) micro-electrolysis technique was used to degrade residual functionalized ILs, 1-butyl-3-methyl benzimidazolium bromide ([BMBIM]Br) and 1-allyl-3-methylimidazolium chloride ([AMIM]Cl) in aqueous solution, and the degradation degree, degradation kinetics and possible degradation pathways were investigated. It was shown that the degradation of these functionalized ILs was highly efficient in the US-ZVI/AC system, and the degradation degree was as high as 96.1% and 92.9% in 110 min for [BMBIM]Br and [AMIM]Cl, respectively. The degradation of [BMBIM]Br could be described by the second-order kinetics model, and [BMBIM]⁺ was decomposed in two ways: (i) sequential cleavage of N-alkyl side chain of the cation produced three intermediates; (ii) the 2-positioned H atoms of the benzimidazolium ring were first oxidized, and then the imidazolium ring was opened. The degradation of [AMIM]Cl followed the first-order kinetics rule, and the 2,4,5-positioned H atoms of the imidazolium ring were oxidized to induce ring opening. In addition, the removal of total organic carbon was found to be >87%, which indicates that most of the ILs was mineralized in the degradation process. These results suggest that ultrasound-assisted ZVI/AC micro-electrolysis is highly effective for the removal of residual functionalized ILs from aqueous environment.