Hyo Kang

We investigated the effect of change in alkyl chain length of cation in tributylalkylphosphonium 3-sulfopropyl methacrylate ([P_444#][C₃S], # = 4, 6, and 8) ionic liquids (ILs) on their osmolality and recovery properties as the draw solute in the forward osmosis (FO) process. The ILs aqueous solutions exhibited a characteristic of the lower critical solution temperature (LCST)-type phase separation, which allowed for the easy recovery of the draw solute or clean water from the diluted draw solution. The LCSTs of 31, 26, 22, and 18 °C were obtained from 2.5, 5.0, 7.5, and 10.0 wt% aqueous solutions of [P₄₄₄₆][C₃S]. When deionized water, 2000 ppm NaCl solution, and 10.0 wt% orange juice aqueous solution were used as feed solution, the water fluxes of the aqueous [P₄₄₄₆][C₃S] solutions were approximately 4.49, 3.87, and 1.55 LMH, respectively, in the active layer facing the draw solution mode at 7.5 wt% of draw solution. This study demonstrates the applicability of a thermoresponsive ionic structure material as a draw solute for the FO process.

The applicability of ionic liquids (ILs) as the draw solute in a forward osmosis (FO) system was investigated through a study on the effect of the structural change of the anion on the FO performance. This study evaluated ILs composed of tetrabutylphosphonium cation ([P₄₄₄₄]⁺) and benzenesulfonate anion ([BS]⁻), para-position alkyl-substituted benzenesulfonate anions (p-methylbenzenesulfonate ([MBS]⁻) and p-ethylbenzenesulfonate ([EBS⁻]), and methanesulfonate anion ([MS]⁻). The analysis of the thermo-responsive properties suggested that the [P₄₄₄₄][MBS] and [P₄₄₄₄][EBS] ILs have lower critical solution temperatures (LCSTs), which play a beneficial role in terms of the reusability of the draw solute from the diluted draw solutions after the water permeation process. At 20 wt% of an aqueous solution, the LCSTs of [P₄₄₄₄][MBS] and [P₄₄₄₄][EBS] were approximately 36 °C and 25 °C, respectively. The water flux and reverse solute flux of the [P₄₄₄₄][MBS] aqueous solution with higher osmolality than [P₄₄₄₄][EBS] were 7.36 LMH and 5.89 gMH in the active-layer facing the draw solution (AL-DS) mode at osmotic pressure of 25 atm (20 wt% solution), respectively. These results indicate that the [P₄₄₄₄]⁺-based ionic structured materials with LCST are practically advantageous for application as draw solutes.

We synthesized various phosphonium- and ammonium-based ionic liquids (ILs), using benzenesulfonate (BS) and 4-methylbenzenesulfonate (MBS) to establish the criteria for designing an ideal draw solute in a forward osmosis (FO) system. Additionally, the effects of monocationic, dicationic, and anionic species on FO performance were studied. Monocationic compounds ([P₄₄₄₄][BS], [P₄₄₄₄][MBS], [N₄₄₄₄][BS], and [N₄₄₄₄][MBS]) were obtained in one step via anion exchange. Dicationic compounds ([(P₄₄₄₄)₂][BS], [(P₄₄₄₄)₂][MBS], [(N₄₄₄₄)₂][BS], and [(N₄₄₄₄)₂][MBS]) were prepared in two steps via a Menshutkin SN₂ reaction and anion exchange. We also investigated the suitability of ILs as draw solutes for FO systems. The aqueous [P₄₄₄₄][BS], [N₄₄₄₄][BS], [N₄₄₄₄][MBS], and [(N₄₄₄₄)₂][BS] solutions did not exhibit thermoresponsive behavior. However, 20 wt% [P₄₄₄₄][MBS], [(P₄₄₄₄)₂][BS], [(P₄₄₄₄)₂][MBS], and [(N₄₄₄₄)₂][MBS] had critical temperatures of approximately 43, 33, 22, and 60 °C, respectively, enabling their recovery using temperature. An increase in IL hydrophobicity and bulkiness reduces its miscibility with water, demonstrating that it can be used to tune its thermoresponsive properties. Moreover, the FO performance of 20 wt% aqueous [(P₄₄₄₄)₂][MBS] solution was tested for water flux and found to be approximately 10.58 LMH with the active layer facing the draw solution mode and 9.40 LMH with the active layer facing the feed solution.