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Dihydrolevoglucosenone (Cyrene™), a Bio-Based Solvent for Liquid-Liquid Extraction Applications Thomas Brouwer, and Boelo Schuur ACS Sustainable Chem

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Dihydrolevoglucosenone (Cyrene™), a Bio-Based Solvent for Liquid-Liquid Extraction Applications Thomas Brouwer, and Boelo Schuur ACS Sustainable Chem Subscriber access provided by UNIV TWENTE Article Dihydrolevoglucosenone (Cyrene™), a Bio-based Solvent for Liquid-Liquid Extraction Applications Thomas Brouwer, and Boelo Schuur ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.0c04159 • Publication Date (Web): 31 Aug 2020 Downloaded from pubs.acs.org on September 16, 2020 Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. 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Page 1 of 42 ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 Dihydrolevoglucosenone (Cyrene™), a Bio-based 8 9 10 11 Solvent for Liquid-Liquid Extraction Applications 12 13 14 15 16 a a,* 17 Thomas Brouwer and Boelo Schuur 18 19 20 21 aSustainable Process Technology group, Process and Catalysis Engineering cluster, 22 23 24 25 Faculty of Science and Technology, University of Twente, Dienerlolaan 5, Meander 26 27 28 building, 7522 NB, Enschede, The Netherlands 29 30 31 32 *corresponding author: Meander building 221, 7522NB, Enschede, The Netherlands, 33 34 35 36 e: [email protected] , p: +31 53 489 2891 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 1 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 2 of 42 1 2 3 4 Abstract 5 6 7 Dihydrolevoglycosenone, commercially known as Cyrene™, is a versatile bio-based 8 9 10 11 solvent reported for various applications including being a medium of chemical 12 13 14 reactions and membrane manufacture. In this work, application of Cyrene™ in liquid- 15 16 17 18 liquid extractions has been investigated. Four ternary systems have been assessed at 19 20 21 298.15K, 323.15K and 348.15K, keeping CyreneTM and methylcyclohexane constant 22 23 24 25 and changing the third compound to toluene, cyclohexanol, cyclohexanone and 26 27 28 cyclopentyl methyl ether. Studying these selected ternary systems, yielded an 29 30 31 indication of applicability of Cyrene™ in related industrial separation processes such 32 33 34 35 as aromatic/aliphatic separations, and in separations of oxygenates in the cyclohexane 36 37 38 oxidation process. Key factors are biphasic system formation, distribution coefficients 39 40 41 42 and selectivity. All ternary systems showed type I liquid-liquid phase behavior with a 43 44 45 selective extraction of ternary components from methylcyclohexane by Cyrene™. The 46 47 48 49 highest selectivity at 298.15K was found for cyclohexanol with 61.4±4.33, followed by 50 51 52 cyclohexanone with 44.1±8.63, while toluene and cyclopentyl methyl ether had a 53 54 55 56 selectivity of respectively 12.0±0.89 and 6.4±0.08. Although CyreneTM is applicable in 57 58 59 all four ternary systems, the miscibility gap is narrow for the oxygenated species, 60 2 ACS Paragon Plus Environment Page 3 of 42 ACS Sustainable Chemistry & Engineering 1 2 3 4 indicating a limited operation window for liquid-liquid extraction which will be more 5 6 7 severe at higher temperatures. Overall, the studies showed that there are certainly 8 9 10 11 application windows for Cyrene™. In the case of oxygenate extraction, a process with 12 13 14 Cyrene™ appears energy-saving because the energy duty appears to be lower than 15 16 17 18 when using water, the best alternative solvent, which is a low boiling solvent for this 19 20 21 purpose. 22 23 24 25 TM 26 KEYWORDS: Dihydrolevoglucosenone, Cyrene , Bio-based Solvent, Liquid-Liquid 27 28 29 30 Equilibrium, Liquid-Liquid Extraction 31 32 33 34 Introduction 35 36 37 Insights in the liquid-liquid extraction (LLX) applicability of dihydrolevoglycosenone, 38 39 40 41 or Cyrene™, was obtained by performing LLX in four different ternary systems. 42 43 44 CyreneTM, a bio-based polar solvent, attracted recent attention as being versatile for 45 46 47 1-7 48 various applications, e.g. as a medium to perform chemical reactions and to prepare 49 50 51 membranes by phase inversion8, though no mention for LLX applications has been 52 53 54 55 found as of yet. 56 57 58 59 60 3 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 4 of 42 1 2 3 TM 1, 8 4 Cyrene can be an alternative aprotic dipolar solvent , solvents of this class are 5 6 7 typically used in a range of molecular separations, from aromatic/aliphatic separation9- 8 9 10 11 12 11 to carboxylic acid separation from water. Industrially important members of the 12 13 14 solvent class of aprotic dipolar solvents include N-methylpyrrolidone (NMP) and N,N- 15 16 17 18 dimethylformamide (DMF), which both are considered toxic solvents and subject to 19 20 21 restrictive legislation. 13-15 CyreneTM is reported to have a much lower toxicity16-17, and 22 23 24 25 additionally since it is a biobased product, it offers chances for the chemical industry 26 27 28 to reduce the consumption of fossil oil by replacing their toxic fossil oil-based solvents 29 30 31 for a much more benign biobased alternative.18 In a recent communication, the Circa 32 33 34 35 Group announced a production capacity of CyreneTM of 1 kton per annum, which 36 37 38 signifies the mass production of this new biobased solvent.19 Although, bulk prices may 39 40 41 42 not be publically available, Krishna et al. state that the bulk price of CyreneTM may be 43 44 45 approximately to be 2 €/kg 20 which is comparable with traditional solvents. 46 47 48 49 Two key classes of molecular separation processes using solvents include extractive 50 51 52 distillation (ED) and LLX. In another article21, we showed the potential of Cyrene™ as 53 54 55 56 entrainer in ED of aromatic/aliphatic mixtures and paraffin/olefin mixtures. Similarly, 57 58 59 next to the already proven entrainer function in extractive distillations, Cyrene™ may 60 4 ACS Paragon Plus Environment Page 5 of 42 ACS Sustainable Chemistry & Engineering 1 2 3 4 be useful for LLX as well. In order to investigate the applicability of Cyrene™ in LLX 5 6 7 processes, we assessed the liquid-liquid equilibrium (LLE) behavior of several ternary 8 9 10 11 systems formed with Cyrene™. The investigated systems include (1) 12 13 14 methylcyclohexane (MCH) and toluene (TOL), (2) MCH and cyclohexanol (CHOH), (3) 15 16 17 18 MCH and cyclohexanone (CHO) and (4) MCH and cyclopentyl methyl ether (CPME). 19 20 21 The molecular structures of all species used in this study are displayed in figure 1. 22 23 24 OH O O 25 O 26 27 28 29 30 O 31 O 32 33 34 35 methylcylohexan toluene Cyclohexanol cyclohexanone Cyclopenthyl Dihydrolevoglucose- 36 e methyl ether none 37 (MCH) (TOL) (CHOH) (CHO) (CPME) (CyreneTM) 38 39 40 Figure 1. Structures of the molecules used in this study. 41 42 43 44 These ternary mixtures have specifically been chosen to firstly represent 45 46 47 aromatics/aliphatics separations. These separations using LLX has been subject of 48 49 50 51 study for a variety of model compounds, including benzene, toluene, xylenes, 52 53 54 (methyl)cyclohexane and n-alkanes.22-27 The model systems vary as the related 55 56 57 58 industrial mixture is complex.28 The results in this study on liquid-liquid equilibria with 59 60 5 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 6 of 42 1 2 3 TM 4 Cyrene , MCH and TOL will be compared to the elaborate work done in the past 5 6 7 concerning molecular solvents22-24, ionic liquids (ILs)25, 29-30 and deep eutectic solvents 8 9 10 31-33 11 (DESs). 12 13 14 The separation of alcohols and ketones from aliphatics was chosen because the 15 16 17 18 compounds possess either an alcohol or a ketone functionality, and they are relevant 19 20 21 industrial chemicals, for example in the industrial oxidation process of cyclohexane to 22 23 24 34-35 25 CHO and CHOH . Kim et al. and Pei et al. investigated similar systems with CHO 26 27 28 and CHOH, though used cyclohexane as hydrocarbon and studied dimethyl sulfoxide 29 30 31 (DMSO) and water as a solvent.36-37 32 33 34 35 The last ternary mixture with MCH and CPME was chosen for the CPME ether 36 37 38 functionality.
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