Dihydrolevoglucosenone (Cyrene), a Biobased Solvent for Liquid–Liquid Extraction Applications

Abstract

Dihydrolevoglycosenone, commercially known as Cyrene, is a versatile biobased solvent reported for various applications including being a medium of chemical reactions and membrane manufacture. In this work, application of Cyrene in liquid–liquid extractions has been investigated. Four ternary systems have been assessed at 298.15 K, 323.15 K, and 348.15 K, keeping Cyrene and methylcyclohexane constant and changing the third compound to toluene, cyclohexanol, cyclohexanone, and cyclopentyl methyl ether. Studying these selected ternary systems yielded an indication of applicability of Cyrene in related industrial separation processes such as aromatic/aliphatic separations and in separations of oxygenates in the cyclohexane oxidation process. Key factors are biphasic system formation, distribution coefficients, and selectivity. All ternary systems showed type I liquid–liquid phase behavior with a selective extraction of ternary components from methylcyclohexane by Cyrene. The highest selectivity at 298.15 K was found for cyclohexanol with 61.4 ± 4.33, followed by cyclohexanone with 44.1 ± 8.63, while toluene and cyclopentyl methyl ether had a selectivity of, respectively, 12.0 ± 0.89 and 6.4 ± 0.08. Although Cyrene is applicable in all four ternary systems, the miscibility gap is narrow for the oxygenated species, indicating a limited operation window for liquid–liquid extraction which will be more severe at higher temperatures. Overall, the studies showed that there are certainly application windows for Cyrene. In the case of oxygenate extraction, a process with Cyrene appears energy-saving because the energy duty appears to be lower than when using water, the best alternative solvent, which is a low boiling solvent for this purpose.

Hydrophobic Deep Eutectic Solvents for the Recovery of Bio-Based Chemicals: Solid–Liquid Equilibria and Liquid–Liquid Extraction

“…Numerous examples of bio-derived organic solvents that can replace traditional fossil-based organic solvents are known. Limonene (derived from citrus peel) has been shown to replace toluene in the cleaning sector [23] or to break azeotrope in the diisopropyl ether/acetone vaporliquid equilibrium [24]; other examples of bio-based solvents are γ-valerolactone [25], 2-methyltetrahydrofuran [26], and dihydrolevoglucosenone (Cyrene) [27,28], among others [3,22].…”

8‐Prenylflavanones through Microwave Promoted Tandem Claisen Rearrangement/6‐endo‐trig Cyclization and Cross Metathesis

“…Recently, dihydrolevoglucosenone, also known under the trade name cyrene®, has attracted considerable attention as a non‐toxic bio‐based polar aprotic solvent with a very high boiling point ( T = 203 °C). [ 31 ] Although it has found several applications as a reaction medium [ 32 ] or for liquid‐liquid extractions [ 33 ] it has apparently not been used as a solvent for microwave accelerated reactions thus far and no information about the stability under these conditions is available. In general, information about the stability of cyrene under various conditions is scarce.…”

Comparison of solvent‐based affinity separation processes using Cyrene and Sulfolane for aromatic/aliphatic separations

“…The UNIQUAC description of the MCH–TOL–Cyrene ternary LLE, seen in Fig. 7, was published by Brouwer and Schuur, 9 in which also the thermodynamic consistency was shown, and the UNIQUAC correlations are presented in Table 5. Additionally, the applied interaction parameters with water are presented.…”

“…While in the further future the use of bio‐crudes might have a significant impact, further greening of traditional industrial crude processing should also be pursued to reduce environmental impacts. Part of this can be realized by increasing the energy efficiency of these processes, 7 and additionally by replacing traditional solvents with bio‐based solvents 8,9 …”

“…A very limited number of binary interaction parameters are currently available for Cyrene. Hence, it was not possible to properly simulate processes of complex crude mixtures, and therefore the study was limited to a model system comprised of one aromatic compound (toluene, TOL) and one aliphatic compound (methylcyclohexane, MCH), for which the parameters have recently been reported 8,9 . Both LLX and ED processes were compared, and we report here on their process configurations, simulation results and corresponding costs.…”