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The distribution coefficients and selectivities required for extraction purposes were predicted with a thermodynamic equation of state for the ternary system formic acid/water/extraction solvent. These predictions were validated with experimental data from the literature and experimental data from the oxidation of biomass to formic acid process measured in this work. Extraction solvents discussed in this work are 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, ethyl n -butyl ether, diisopropyl ether, di- n -butyl ether, benzyl formate, and heptyl formate. The considered temperature ranged from 273 to 363 K under atmospheric pressure. Perturbed-chain statistical associating fluid theory (PC-SAFT) was used for prediction purposes applying an approach as simple as possible and as complex as necessary to achieve trustworthy data for selecting the best extraction solvent. Using PC-SAFT allowed identifying 1-hexanol as the most promising solvent out of the 11 extraction agents. The predicted data were in good agreement with the experimental distribution coefficients and the selectivities, which are very sensitive to experimental uncertainties.

Measuring and Predicting the Extraction Behavior of Biogenic Formic Acid in Biphasic Aqueous/Organic Reaction Mixtures