Efficiency of hydrophobic phosphonium ionic liquids and DMSO as recyclable cellulose dissolution and regeneration media

Hydrophobic, long-chain tetraalkylphosphonium acetate salts (ionic liquids) were combined with a dipolar aprotic co-solvent, dimethylsulfoxide (DMSO), and the feasibility of these solvent systems for cellulose dissolution and regeneration was studied. A 60 : 40 w/w mixture of the ionic liquid tetraoctylphosphonium acetate ([P₈₈₈₈][OAc]) and DMSO was found to dissolve up to 8 wt% cellulose, whilst trioctyl(tetradecyl)phosphonium acetate ([P₁₄₈₈₈][OAc]) dissolved up to 3 wt% cellulose. Water (an anti-solvent for cellulose) was found to give rise to biphasic liquid-liquid systems when combined with these mixtures, yielding an upper phase rich in ionic liquid and a lower aqueous phase. The liquid-liquid equilibria of the ternary systems were experimentally determined, finding that DMSO strongly partitioned towards the aqueous phase. Thus, a process scheme involving simultaneous regeneration of cellulose and recycling of the solvent system was envisioned, and demonstrated on a large scale using [P₈₈₈₈][OAc]. A large portion of the ionic liquid (ca. 60 wt%) was directly recovered via phase separation, with a further 37 wt% being recovered from the swollen cellulose phase and residual materials, bringing recovery to 97%. XRD analysis of the recovered cellulose materials showed a loss of crystallinity and conversion from Cellulose I to Cellulose II. Non-dissolving compositions of ionic liquid and DMSO did not affect cellulose crystallinity after cellulose pulp treatment.