BACKGROUNDConventional methods for the separation of 1,3‐propanediol (1,3‐PDO) are problematic in many ways. The study of simple and efficient separation process was the key to solving the bottlenecks that restricted the large‐scale development of 1,3‐propanediol. In order to solve the difficulty of separating 1,3‐propanediol from fermentation broths, a ternary selective extraction system was constructed to separate 1,3‐propanediol from the simulated solution and fermentation broth.RESULTSIn this study, the quantum chemistry calculation and wave function analysis showed that the reaction between phenylboronic acid and 1,3‐PDO is thermodynamically feasible, stable, and covalently reversible. The ternary extraction system composed of 1‐naphthylboric acid, dichloromethane and Aliquate®336. After optimization of the extraction conditions, a high extraction efficiency of 82.6% could be achieved for 1,3‐PDO. Meanwhile, a stripping recovery of 1,3‐PDO was over 90% with a high purity of 1,3‐PDO (98.6%) from a simulated solution using 0.4 M of hydrochloric acid as stripping solution. The extraction selectivity of 1,3‐PDO to glycerol, acetic acid and butyric acid in the fermentation broth reached to 12.9, 230.6, 233.7, respectively, implying a high selective performance compared with the aldehyde‐based traditional reactive extraction.CONCLUSIONSThe ternary extraction system exhibited good extraction performance which highlighted potential for selective extraction of diol biochemicals from fermentation broths.This article is protected by copyright. All rights reserved.