Liquid-liquid equilibrium in systems used for the production of 5-hydroxymethylfurfural from biomass using alcohols as solvents

https://doi.org/10.1016/j.jct.2017.03.019Get rights and content

Highlights

  • New LLE data were determined for the systems containing water + 5-HMF + alcohols.

  • 5-HMF distributed similarly for 1-butanol and 2-pentanol but little in 2-butanol.

  • 2-pentanol is better than 1-butanol or 2-butanol to separate 5-HMF from water.

  • A fully description of uncertainty determination was provided.

  • The NRTL model represented the solubility curves with accuracy.

Abstract

The present work reports liquid–liquid equilibrium data for systems containing water + 5-hydroxymethylfurfural + {1-butanol, 2-butanol or 2-pentanol} at T = 298.2 K and atmospheric pressure (∼0.1 MPa), determined by refractometry and density measurements. The results were evaluated by calculation of the overall mass balance, resulting in overall relative deviations lower than 1.05%. Experimental data were correlated with the NRTL model to calculate the activity coefficient. The average root mean square deviation was equal to 0.65% for all systems. Cloud points, tie lines, partition coefficients and selectivities indicated that 2-pentanol is better than the other studied solvents for 5-hydroxymethylfurfural recovery from water.

Introduction

Biorefineries are becoming part of the policies and strategies of countries and companies around the world due to the need for sustainable and renewable energy sources in the near future. However, there are technical/scientific bottlenecks related to the understanding of potential routes to bulk chemicals from biomass, similar to the value chains of petroleum derivatives.

Bioethanol – the only renewable liquid fuel currently produced in large quantities – presents some limitations including: low net heat of combustion, low vapor pressure and contamination by water absorption from the atmosphere [1]. Such limitations may restrict the direct substitution of derived petrol fuels, mainly gasoline, and have instigated many researchers to develop alternative processes for production of biofuels through catalytic chemical conversion of biomass. Two biofuels recently studied are 2,5–dimethylfuran (DMF) and 2–methylfuran (MF). Both DMF and MF, together with a wide range of chemical intermediates and end–products, are produced from 5–hydroxymethylfurfural (HMF), which can be considered a key compound in biorefining [2], [3], [4], [5].

HMF can be produced in different reaction media, which can be composed by water, organic solvents, halide salts, ionic liquids (ILs), sub– and supercritical fluids, and their mixtures [1], [2], [6], [7], [8], [9], [10], [11], [12], [13], [14], [15], [16]. Román-Leshkov and Dumesic [7] studied the use of inorganic salts to saturate the reactive aqueous phase of the biphasic system and therefore alter the extraction equilibrium of HMF. The introduction of salts promoted an increase in HMF selectivity, and also the formation of biphasic systems by solvents that are otherwise completely miscible with water, such as 1–propanol.

Technological advances in furan biofuel production from plant biomass– derived sugars were reported by Román–Leshkov et al. [1], [8], which detailed the dehydration process of fructose by acid catalysis to produce 5-hydroxymethylfurfural (HMF) in two liquid phases in a biphasic reactor. The reactive aqueous phase in the biphasic reactor contains an acid catalyst and fructose, and the extracting phase contains a water-immiscible organic solvent that continuously extracts the HMF from the aqueous phase. According to Liu et al. [9], the purification process of HMF from aqueous reaction medium remains a challenge. Okano et al. [16] obtained an efficient aqueous–acetonitrile biphasic system established for dehydration of fructose to HMF in the presence of acidic ILs, and they presented an experimental pseudo ternary phase diagram of the acidic ionic liquid + water + acetonitrile system with tie lines at room temperature. In this subject, our research group published the liquid–liquid equilibria of ternary systems containing water + DMF + alcohols [17].

Detailed study of liquid-liquid equilibrium (LLE) for extraction of HMF formed in aqueous systems by contact with an organic solvent is considered a fundamental step for optimizing the purification of furan derivatives (MF and DMF). Phase equilibrium of binary systems containing DMF have recently been published [18], [19], [20], [21], [22]. However, a literature search indicated that no thermodynamic data are available for the investigated ternary systems related to HMF, water and alcohols measured in this work until the present date. Moreover, phase equilibrium data plays an important role for the thermodynamic modeling and scale–up of extraction processes since it provides fundamental information to support computer simulation. Therefore, this work presents the apparatus and experimental procedures applied to quantify the phase compositions for LLE ternary systems formed by water + 5-hydroxymethylfurfural + {1-butanol, 2–butanol or 2-pentanol} at T = 298.2 K and atmospheric pressure (∼0.1 MPa). Such butanols were selected because they are environmentally benign solvents and exhibit desirable properties for HMF extraction from the reactive media aqueous phase [1], [6], [7], [8]. Experimental data were modeled using the well-known non-random two-liquid model (NRTL) [23].

Section snippets

Materials

The reagents used in this work and their determined properties are presented in Table 1 together with literature values [24], [25]. HMF and alcohols were used as purchased from the supplier Sigma Aldrich (USA), without further purification. 2-butanol and 2-pentanol used in this work are racemic mixtures. Distilled water was obtained from Quimis Q341 distiller (Brazil).

Determination of binodal curves

Preliminary information about immiscibility region is provided by the knowledge of binodal curves, determined through cloud

Liquid-liquid equilibrium

The components studied in this work received the following notation: water (1), 5-hydroxymethylfurfural (2), 1-butanol (3), 2-butanol (4) and 2-pentanol (5). Cloud point data in mass fractions, densities and refractive indices for the three ternary systems studied are presented in Table 2, and the binodal curves are shown in the form of a triangular diagram in Fig. 1. As can be observed, these systems can be regarded as a “pseudo” type I according to Treybal’s nomenclature [38], since for the

Conclusions

New experimental liquid-liquid equilibrium data for water + HMF + {1-butanol, 2-butanol or 2-pentanol} ternary systems were determined at T = 298.2 K. Binodal curves, tie lines, partition coefficients and selectivities related to extraction of HMF were also experimentally determined. Type I behavior was found for all systems and low deviations were obtained for the overall mass balance. For the studied systems, HMF showed similar preference for the organic phase when 1-butanol or 2-pentanol were used

Acknowledgements

This work is dedicated to Professor Dr. Martín Aznar, whose life was prematurely taken from us. Professor Aznar will remain as a reference scientist, an example of courage, always enlightening us with his kindness, experience and creativeness. The authors gratefully acknowledge the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP/Brazil) for the financial support and scholarships, specifically Irede Dalmolin through the FAPESP process 2013/14118-3, Luis A. Follegatti-Romero through

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    Current address: Academic Department of Chemical Engineering, Federal Technological University of Paraná, Linha Santa Bárbara s/n, 85601-970 Francisco Beltrão, PR, Brazil.

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