Characterization of pH dependence in organic acid absorption with non-reactive and reactive polymers for application in two-phase partitioning bioreactors

• Species distribution clearly described during acid partitioning in an absorptive polymer.
• Effect of acid absorption on equilibrium pH well characterized.
• High pressure CO2 (60 bar) can reversibly lower pH to facilitate acid absorption.
• Amine-functionalized hydrogels achieve high acid recovery with low polymer fractions.

Strategies for extracting organic acids from aqueous solutions using polymeric absorbents are demonstrated and discussed in the context of two-phase partitioning bioreactor (TPPB) design. Experimental data and material balances for the uptake of butyric acid and benzoic acid by a poly(ether-block-amide) copolymer (Pebax 2533) establish the inherent limitations of unreactive absorbents for organic acid bioprocesses that operate at near-neutral pH. Improvements to TPPB performance are achieved by lowering pH temporarily with CO2 to enhance acid absorption, and removing the solute-rich polymer before restoring pH to fermentative values by releasing the CO2 pressure. Butyric acid removal by Pebax 2533 improved from 3% to 40% upon acidifying a pH 6 solution with 60 bar of CO2, while benzoic acid absorption increased from 1% to 80% using this pressure manipulation technique. A reactive extraction approach involving a newly-synthesized amine functionalized hydrogel is also described wherein acid/base reaction equilibrium governs the extent of solute uptake. Copolymerization of 2-(dimethylamino)ethyl acrylate (DMAEA) and trimethylolpropane triacrylate (TMPTA) yielded a thermoset material with sufficient basicity to remove 80% of both butyric and benzoic acid from aqueous solution using just 1 wt% polymer relative to the aqueous phase mass.