Systematic Identification of Solvents Optimal for the Extraction of 5-Hydroxymethylfurfural from Aqueous Reactive Solutions

To ensure a high efficiency of 5-hydroxymethylfurfural (HMF) synthesis, improved solvents for the extraction of HMF from a reactive aqueous solution were identified using the predictive thermodynamic model COSMO-RS. Utilizing COSMO-RS as a basis for a systematic solvent selection has the advantage of potentially saving significant time and effort by computationally screening several thousand possible solvents. Factors including temperature, concentration, and fructose addition were used for experimental validation of the predictive power of COSMO-RS. Continuous extraction experiments confirmed also kinetics and phase separation to be important for technical implementation. COSMO-RS predicted o-propylphenol and o-isopropylphenol to have partition coefficients as high as 10.02 and 9.82, which are roughly five times higher than the partition coefficient of the previously known, most effective solvent: 2-methyltetrahydrofuran (PHMF = 2). Therefore, the identification of o-propylphenol and o-isopropylphenol as...

[1]  A. Klamt.  Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena , 1995 .

[2]  Kai Leonhard,et al.  Cellulose and hemicellulose valorisation: an integrated challenge of catalysis and reaction engineering , 2014 .

[3]  Felix H. Richter,et al.  Set of Acidic Resin Catalysts To Correlate Structure and Reactivity in Fructose Conversion to 5-Hydroxymethylfurfural , 2013 .

[4]  James A. Dumesic,et al.  Production of levulinic acid and gamma-valerolactone (GVL) from cellulose using GVL as a solvent in biphasic systems , 2012 .

[5]  Alessandro Gandini,et al.  Furans in polymer chemistry , 1997 .

[6]  Petr Kolář,et al.  Solvent selection for pharmaceuticals , 2002 .

[7]  Changwei Hu,et al.  Catalytic conversion of glucose to 5-hydroxymethylfurfural over SO42−/ZrO2 and SO42−/ZrO2–Al2O3 solid acid catalysts , 2009 .

[8]  Johnathan E. Holladay,et al.  Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural , 2007, Science.

[9]  Stephanie G. Wettstein,et al.  Production of biofuels from cellulose and corn stover using alkylphenol solvents. , 2011, ChemSusChem.

[10]  James A. Dumesic,et al.  Solvent Effects on Fructose Dehydration to 5-Hydroxymethylfurfural in Biphasic Systems Saturated with Inorganic Salts , 2009 .

[11]  C. Afonso,et al.  5-Hydroxymethylfurfural (HMF) as a building block platform: Biological properties, synthesis and synthetic applications , 2011 .

[12]  Yuriy Román‐Leshkov,et al.  Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates , 2007, Nature.

[13]  S. S. Rath,et al.  Multicomponent Liquid−Liquid Equilibria Prediction for Aromatic Extraction Systems Using COSMO-RS , 2007 .

[14]  de Ab André Haan,et al.  COSMO-RS-based extractant screening for phenol extraction as model system , 2008 .

[15]  Yuriy Román-Leshkov,et al.  Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose , 2006, Science.

[16]  M. Yasukawa,et al.  Simplified model for extraction of 5-hydroxymethylfurfural from fructose: Use of water/oil biphasic system under high temperature and pressure conditions , 2013 .

[17]  James A. Dumesic,et al.  Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides , 2007 .

[18]  K. Leonhard,et al.  Illustrating Computational Solvent Screening : Prediction of Standard Gibbs Energies of Reaction in Solution , 2008 .

[19]  S. Singh,et al.  Template-directed approach to solid-phase combinatorial synthesis of furan-based libraries☆ , 2002 .

[20]  James A. Dumesic,et al.  Conversion of hemicellulose to furfural and levulinic acid using biphasic reactors with alkylphenol solvents. , 2012, ChemSusChem.

[21]  Xiaohong Wang,et al.  Conversion of fructose and glucose into 5-hydroxymethylfurfural catalyzed by a solid heteropolyacid salt , 2011 .

[22]  Jochen Büchs,et al.  Prediction of partition coefficients using COSMO-RS: Solvent screening for maximum conversion in biocatalytic two-phase reaction systems , 2008 .

[23]  Basudeb Saha,et al.  Advances in 5-hydroxymethylfurfural production from biomass in biphasic solvents , 2014 .

[24]  Kai Leonhard,et al.  Screening of new solvents for artemisinin extraction process using ab initio methodology , 2010 .

[25]  James A. Dumesic,et al.  Production of 5-Hydroxymethylfurfural from Glucose Using a Combination of Lewis and Brønsted Acid Catalysts in Water in a Biphasic Reactor with an Alkylphenol Solvent , 2012 .

[26]  A. Klamt,et al.  Refinement and Parametrization of COSMO-RS , 1998 .

[27]  C. McNeff,et al.  Continuous production of 5-hydroxymethylfurfural from simple and complex carbohydrates , 2010 .