Quaternary and ternary LLE measurements for solvent (2-methyltetrahydrofuran and cyclopentyl methyl ether) + furfural + acetic acid + water between 298 and 343 K
Graphical abstract
Introduction
There is a growing demand for more active use of bio-based materials and chemicals due to the increasing concerns for the environment and the increasing greenhouse gas emissions produced by the fossil-source based production methods. To facilitate this goal, various bioprocesses have been studied for the production of chemicals that could substitute fossil-based matter in synthesis of, for example, pharmaceuticals, solvents and even fuels. One bio-component that has received increasing attention is furfural, which can be produced from xylose via dehydration in bioreactors. Furfural production is hindered by decomposition [1], [2], [3] as well as the side-reactions furfural undertakes in reactor conditions [4]. Furfural is utilized in the industry as a solvent for lubrication oil production industry [5] and as a raw material for some pharmaceuticals [6]. There have also been suggestions for its potential in production of biofuels [7].
Additionally, an industrial furfural product streams consist mostly of water with circa 5–10 w-% furfural content with a similar weight of acids in the streams. To separate furfural from these streams, various unit operations like membrane separation, adsorption or liquid-liquid extraction have been suggested. Majority of current industrial processes use steam distillation to separate furfural. However, this is energy intensive and limited by the minimum boiling azeotrope between furfural and water. Membrane processes have shown promise for the separation; however, their maturity is not yet at a stage where large scale industrial applications are reasonable. Adsorption is a promising technology as well; however, majority of the studies focus mostly on the absorption research, leaving the desorption research somewhat lacking. Liquid-liquid extraction has been proposed to be currently the most energy efficient method for furfural removal from aqueous streams through either biphasic reactors or extraction units.
To facilitate liquid-liquid extraction, the liquid-liquid equilibria of various solvents with furfural has been studied to determine their ability for selective furfural extraction. Various other solvents ranging from ionic liquids [8] to alcohols [9] and other solvents [10], [11], [12] have also been studied for the extraction of furfural from aqueous ternary mixtures. Such solvents as MTBE [13] (methyl tertbutyl ether), TAME [14] (tert-amyl methyl ether), MIBK [15] (methyl isobutyl ketone), 2-MTHF [16] (2-methyl tetrahydrofuran) and CPME [16] (cyclopentyl methyl ether) have shown great promise in our previous studies, however study of ternary systems involving furfural is not enough alone – the acid content of the feed needs to be addressed as well. To this end, ternary and quaternary measurements involving both furfural and acetic acid with the solvents and water provide necessary data for accurate solvent assessment. CPME has additionally been reported to have a low tendency for peroxide formation, an issue often met when dealing with ethers, and a relatively good stability in acidic conditions [17].
In our earlier work with TAME [14], the ternary system with acetic acid shows a tendency towards concentrating the acid in the aqueous phase, which is a desired feature for the solvent. Due to the high affinity of CPME for furfural shown in earlier work [16], determination of the behavior of the two solvents studied in that work (2-MTHF and CPME) towards acetic acid is paramount. This work provides novel quaternary and ternary LLE data and model parameters along with distribution factors and selectivities for studied solutes in 2-MTHF and CPME. The obtained data is compared to other solvents to assess the suitability of 2-MTHF and CPME to furfural extraction in ternary and quaternary mixtures.
Section snippets
Materials
All the chemicals used were purchased from Sigma-Aldrich, except for the analytical acetone, which was purchased from Merck and the water, which was purified in-house with a Millipore Milli-Q system. Manufacturer reported purities were checked with a gas chromatograph analysis. The manufacturer specified furfural (CAS: 98-01-1, MW: 96.08 g/mol) at a purity of 99 wt-%, and it was further distilled to obtain a purity of 99.90 wt-%. 2-MTHF (CAS: 96-47-9, MW: 86.13 g/mol) was specified at a purity
Results and discussion
The developed response factors and the known mass of the internal standard were used to calculate the masses of each individual component in the mixture from the GC peak areas. The masses and mass fractions were calculated with Eqs. (1), (4) and their uncertainties with Eqs. (5), (6). The details of the methodology were explained in earlier work [13].
The
Conclusions
Novel ternary and quaternary data on systems involving acetic acid, furfural, water and solvents 2-MTHF and CPME were measured in temperatures between 298 and 343 K. The systems were modeled using UNIQUAC-HOC activity coefficient model with additional binary interaction parameters regressed for acetic acid. The models provided a good fit for both the ternary systems and the quaternary systems studied. Calculation of the selectivities and distribution coefficients of these solvents towards
Author contributions
The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.
Funding sources
The authors would like to acknowledge the Academy of Finland (Suomen Akatemia, decision number 253336) for their financial support. Mikael Männistö would also like to acknowledge Fortum Foundation for their support.
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