The aim of this work was to recover a mixture of carboxylates ranging from 2 to 7 carbon atoms using a strong anion exchange resin, followed by desorption with CO₂-expanded methanol. Medium chain carboxylates hexanoate and heptanoate adsorbed better than acetate, and the corresponding medium chain carboxylic acids desorbed easier than acetic acid. Consequently, hexanoate and heptanoate were concentrated up to 14.6 and 20.7 times, respectively. These findings will enable effective separation and purification of the produced carboxylic acids. Notably, the presence of inorganic ions in the sample, such as chloride, decreased the adsorption affinity compared to a synthetic mixture only of carboxylates.

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Production of bio-based acetate is commonly hindered by the high costs of the downstream processing. In this paper, a model is developed to describe a new method that recovers acetate salts using anion exchange resins, and subsequently desorbs and upgrades them using CO2-expanded alcohol. The model consists of equilibrium parameters for both the adsorption and desorption step. The calculated parameters are: for the adsorption KCl- Ac- =0.125, KCl- HCO3 - =0.206 and KOV,HAc=0.674[Formula presented], and for the desorption pKMeCO3 - Ac- =3.71. The maximum experimental concentration of acetic acid obtained in CO2-expanded methanol is 0.427 mol/kg (20 g/LMeOH) at an operating pressure of 31 bar. The model represents the expected trends for all species, and can be used to design a multicolumn system for the recovery and upgrading of carboxylates.

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The recovery of carboxylic acids from fermentation broth is one of the main bottlenecks for the industrial production of bio-based esters. This paper proposes an alternative for the recovery of carboxylates produced by fermentations at pH values above the pKa of the carboxylic acid. In this approach, the aqueous carboxylate anion is recovered using anion exchange, followed by desorption and esterification with CO2-expanded alcohols. Using CO2-expanded methanol, we achieved a high desorption yield at 10 bar of CO2 and 20 °C. An ester yield of 1.03 ± 0.07 mol methyl acetate/acetatein was obtained for the combined desorption–esterification at 5 bar of CO2 and 60 °C. The proposed process has low chemical consumption and low waste production. The proposed process works, with a lower yield, for other carboxylates (e.g. lactate and succinate) and alcohols (e.g. ethanol).@en

This paper describes a new option for integrated recovery and esterification of carboxylates produced by anaerobic digestion at a pH above the pKa. The carboxylates (acetate, propionate, butyrate, valerate and lactate) are recovered using a strong anion exchange resin in the bicarbonate form, and the resin is regenerated using a CO2-expanded alcohol technique, which allows for low chemicals consumption and direct esterification. Paper mill wastewater was used to study the effect of pH and the presence of other inorganic anions and cations on the adsorption and desorption with CO2-expanded methanol. Calcium, which is present in paper mill wastewater, can cause precipitation problems, especially at high pH. Esters yields ranged from 1.08 ± 0.04 mol methyl acetate/mol of acetatein to 0.57 ± 0.02 mol methyl valerate/mol of valeratein.@en