Extraction of 5-Hydroxymethylfurfural and Furfural in Aqueous Biphasic Systems: A COSMO-RS Guided Approach to Greener Solvent Selection
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ABSTRACT:
SUBMITTER: Soukup-Carne D
PROVIDER: S-EPMC10915861 | biostudies-literature | 2024 Feb
REPOSITORIES: biostudies-literature
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Project description:Choline chloride (ChCl) / glycolic acid (GA) deep eutectic solvent (DES) media with high water content but without any additional catalyst are introduced in furfural and 5-hydroxymethylfurfural (HMF) production. The effects of water content, reaction time, and reaction temperature are investigated with two feedstocks: a glucose/xylose mixture and birch sawdust. Based on the results, 10 equivalent quantities of water (32.9 wt.%) were revealed to be beneficial for conversions without rupturing the DES structure. The optimal reaction conditions were 160 °C and 10 minutes for the sugar mixture and 170 °C and 10 minutes for birch sawdust in a microwave reactor. High furfural yields were achieved, namely 62 % from the sugar mixture and 37.5 % from birch sawdust. HMF yields were low, but since the characterization of the solid residue of sawdust, after DES treatment, was revealed to contain only cellulose (49 %) and lignin (52 %), the treatment could be potentially utilized in a biorefinery concept where the main products are obtained from the cellulose fraction. Extraction of products into the organic phase (methyl isobutyl ketone, MIBK) during the reaction enabled the recycling of the DES phase, and yields remained high for three runs of recycling.
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Project description:Reactive extraction is an emerging operation in the industry, particularly in biorefining. Here, reactive extraction was demonstrated, enhanced by microwave irradiation to selectively heat the reactive phase (for efficient reaction) without unduly heating the extractive phase (for efficient extraction). These conditions aimed at maximizing the asymmetries in dielectric constants and volumes of the reaction and extraction phases, which resulted in an asymmetric thermal response of the two phases. The efficiency improvement was demonstrated by dehydrating xylose (5 wt % in water) to furfural with an optimal yield of approximately 80 mol % compared with 60-65 mol % under conventional biphasic conditions, which corresponds to approximately 50 % reduction of byproducts.
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Project description:In this work, 502 experimental data for CO2 solubilities and 132 for Henry's constants of CO2 in DESs were comprehensively summarized from literatures and used for further verification and development of COSMO-RS. Large systematic deviations of 62. 2, 59.6, 63.0, and 59.1% for the logarithmic CO2 solubilities in the DESs (1:2, 1:3, 1:4, 1:5), respectively, were observed for the prediction with the original COSMO-RS, while the predicted Henry's constants of CO2 in the DESs (1:1.5, 1:2, 1:3, 1:4, 1:5) at temperatures ranging of 293.15-333.15 K are more accurate than the predicted CO2 solubility with the original COSMO-RS. To improve the performance of COSMO-RS, 502 data points of CO2 solubility in the DESs (1:2, 1:3, 1:4, 1:5) were used for correcting COSMO-RS with a temperature-pressure dependent parameter, and the CO2 solubility in the DES (1:6) was predicted to further verify the performance of the corrected model. The results indicate that the corrected COSMO-RS can significantly improve the model performance with the ARDs decreasing down to 6.5, 4.8, 6.5, and 4.5% for the DESs (1:2, 1:3, 1:4, and 1:5), respectively, and the corrected COSMO-RS with the universal parameters can be used to predict the CO2 solubility in DESs with different mole ratios, for example, for the DES (1:6), the corrected COSMO-RS significantly improves the prediction with an ARD of 10.3% that is much lower than 78.2% provided by the original COSMO-RS. Additionally, the result from COSMO-RS shows that the σ-profiles can reflect the strength of molecular interactions between an HBA (or HBD) and CO2, determining the CO2 solubility, and the dominant interactions for CO2 capture in DESs are the H-bond and Van der Waals force, followed by the misfit based on the analysis of the predicted excess enthalpies.
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Project description:Biphasic systems have received increasing attention for acid-catalyzed dehydration of hexoses to 5-hydroxymethylfurfural (HMF) because of their high efficiency in in situ extraction and stabilization of HMF. Different organic solvents and acid catalysts were applied in these systems, but their effects on the dehydration activity and HMF yield, and the recycling of homogeneous acid catalysts remain largely unexplored. Here, we tested different solvent systems containing a wide range of organic solvents with low boiling points to study the effects of their chemical structures on fructose dehydration and provided stable H2O-dioxane and H2O-acetonitrile biphasic systems with high HMF yields of 76-79% using water-soluble sulfonic derivatives as homogeneous acid catalysts under mild conditions (383 K). By analyzing the partition coefficients of HMF and sulfonic derivatives, 94.3% of HMF and 87.1% of NH2SO3H were, respectively, restrained in the dioxane phase and aqueous phase in the H2O-dioxane biphasic system and easily divided by phase separation. The effects of the adjacent group in sulfonic derivatives and reaction temperature on fructose conversions and HMF yields suggest that in a specific biphasic system, the catalysts' acidity and reaction conditions significantly affect the fructose dehydration activity but hardly influence the optimal yield of HMF, and an almost constant amount of carbon loss was observed mainly due to the poor hydrothermal stability of fructose. Such developments offer a promising strategy to address the challenge in the separation and recycling of homogeneous acid catalysts in the practical HMF production.
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