Purification and concentration of formic acid from formic acid/gluconic acid mixtures by two successive steps of nanofiltration and reactive liquid-liquid extraction

[Display omitted] •Downstream of formic acid from formic acid/gluconic acid diluted mixtures.•First nanofiltration step to separate formic acid and gluconic acid each other.•Second reactive liquid-liquid extraction step to concentrate formic acid.•Efficient separation between both acids and strong concentration of formic acid. A downstream process for the purification and concentration of formic acid (FA) from FA/gluconic acid (GA) mixtures, obtainable by a coupled biocatalytic reaction of CO2 reduction and glucose oxidation, has been developed. The process involved two technologies: (i) a first nanofiltration (NF) step to separate FA and GA, and (ii) a second reactive liquid-liquid extraction (RLLE) step to concentrate FA. The NF process, using a Synder NFX membrane, consisted of three NF steps separated into two divergent lines, named permeate and retentate pathways. The first NF was common for both pathways, resulting in a permeate strongly enriched in FA and depleted in GA, and a retentate with opposite characteristics. In the permeate pathway, this first permeate was subjected to a second NF to obtain a 99.6% pure FA permeate. In the retentate pathway, an additional NF step on the first retentate resulted in a concentrated 99.4% pure GA retentate. The final diluted FA permeate was concentrated by RLLE using tri-N-octylamine as extractant in n-octanol, and a final back-extraction with NaOH. The optimized RLLE process involved a 100-fold volume decrease and resulted in a final FA solution (as sodium formate) of 174.5 g/L, 78 times more concentrated than the feed.