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The present study focuses on the isolation of acetic and lactic acid from a fermentation broth produced by heterofermentative microorganisms using glucose and xylose as substrate. Especially xylose fermentation to lactic acid leads to unwanted by-product formation of acetic acid. Reactive liquid-liquid extraction is an energy-efficient downstream process, where the use of green solvents such as d-limonene opens the way to a more sustainable production. To find the optimum solvent/reactive extractant pairing, the reactive extractants trioctylamine, trioctylphosphine oxide, Aliquat 336, and tributyl phosphate were used diluted in 1-octanol, 1-decanol, d-limonene or a deep eutectic solvent. The phosphine-based extractants proved to be most effective for both acids. In the first extraction step, 19% of acetic acid and only 3% of lactic acid are extracted with trioctylphosphine oxide/1-octanol when the xylose feed is used without pH adjustment. The pKa value of the acids is responsible for the difference in extraction efficiency leading to the proposal of a two-step extraction separating first acetic acid and after pH adjustment, lactic acid can be extracted. The combination of trioctylphosphine oxide diluted in d-limonene leads to a surprisingly high selectivity for lactic acid isolation in the second extraction step. The present study shows for the first time that green solvents lead to similar extraction efficiencies compared to conventional solvents such as 1-octanol. For back extraction n-heptane and p-cymene are used as disintegration agents and water as stripping phase; n-heptane results in a lactic acid back extraction efficiency of up to 82% and p-cymene up to 70%. This shows that also for the back extraction p-cymene as a green disintegration agent leads to similar results as fossil-based n-heptane.

Carboxylic acids can be isolated from fermentation broths using reactive liquid-liquid extraction, offering an alternative to the environmentally harmful state-of-the-art process of precipitating calcium lactate. To enhance the sustainability of liquid-liquid extraction processes, greener solvents, such as natural deep eutectic solvents, are investigated. However, fermentation broths often exhibit pH values unsuitable for carboxylic acid extraction, which can be adjusted using mineral acids, though mineral acids may be co-extracted. In this study, we systematically examine the co-extraction of hydrochloric, nitric, sulfuric, and phosphoric acid during extraction and back-extraction of lactic acid. The solvent phase consisted of tri-n-octylamine, trioctylphosphine oxide, or tributyl phosphate diluted in a thymol-menthol deep eutectic solvent. The back-extraction was conducted using a diluent swing with p-cymene as the antisolvent and water as the receiving phase. Tri-n-octylamine showed the highest efficiency for lactic acid (up to 29.8%) but also the highest co-extraction of mineral acids (up to 50.9%). In contrast, trioctylphosphine oxide exhibited a lower but more selective lactic acid extraction (5.94%) with low mineral acids co-extraction (0.135%). Overall, the highest co-extraction was observed for phosphoric acid and the lowest for nitric acid. In conclusion, the selected solvent phase composition and mineral acid influence the co-extraction and, thus, final product purity. The successful application of the natural deep eutectic solvent as the modifier enhances the sustainability of liquid–liquid extraction processes.