A novel downstream process for highly pure 1,3‐propanediol from an efficient fed‐batch fermentation of raw glycerol by Clostridium pasteurianum

An efficient downstream process without prior desalination was developed for recovering 1,3‐propanediol (1,3‐PDO) with high purity and yield from broth of a highly productive fed‐batch fermentation of raw glycerol by Clostridium pasteurianum. After removal of biomass and proteins by ultrafiltration, and concentration by water evaporation, 1,3‐PDO was directly recovered from the broth by vacuum distillation with continuous addition and regeneration of glycerol as a supporting agent. Inorganic salts in the fermentation broth were crystallized but well suspended by a continuous flow of glycerol during the distillation process, which prevented salt precipitation and decline of heat transfer. On the other hand, ammonium salt of organic acids were liberated as ammonia gas and free organic acids under vacuum heating. The latter ones formed four types of 1,3‐PDO esters of acetic acid and butyric acid, which resulted in yield losses and low purity of 1,3‐PDO (< 80%). In order to improve the efficiency of final 1,3‐PDO rectification, we examined alkaline hydrolysis to eliminate the ester impurities. By the use of 20% (w/w) water and 2% (w/w) sodium hydroxide, > 99% reduction of 1,3‐PDO esters was achieved. This step conveniently provided free 1,3‐PDO and the sodium salt of organic acids from the corresponding esters, which increased the 1,3‐PDO yield by 7% and prevented a renewed formation of esters. After a single stage distillation from the hydrolyzed broth and a followed active carbon treatment, 1,3‐PDO with a purity of 99.63% and an overall recovery yield of 76% was obtained. No wastewater with high‐salt content was produced during the whole downstream process. The results demonstrated that the monitoring and complete elimination of 1,3‐PDO esters are crucial for the efficient separation of highly pure 1,3‐PDO with acceptable yield from fermentation broth of raw glycerol.