Direct conversion of carboxylate salts to carboxylic acids via reactive extraction

by Xin Xu

Institution: Texas A&M University
Year: 2008
Record ID: 1836186
Full text PDF: http://hdl.handle.net/1969.1/86006


The MixAlco process, a proprietary technology owned by Texas A&M University, converts biomass (e.g., municipal solid waste, sewage sludge, paper, agricultural residues, and energy crops) into usable chemicals (e.g., acetic acid) and fuels (e.g., ethanol). Historically, calcium carbonate has been used as the buffer. Recently, it was found that using ammonium bicarbonate as the buffering agent enhances the fermentation conversion. In this case, fermentation broth contains ammonium salts (e.g., ammonium acetate, propionate, butyrate, pentanoate). Therefore, the downstream processing steps (including extraction, purification, esterification, and product separation) must be compatible with the ammonium carboxylate salts formed in the fermentation. This research focuses on converting fermentation broth carboxylate salts into their corresponding acids via "acid springing." Reactive extraction and thermal conversion (distillation) are crucial parts of the acid springing process. Because the components of the fermentation broth are over 80% ammonium acetate and 20% other ammonium carboxylate salts (ammonium propionate, butyrate, pentanoate, etc.), all the initial experiments in this study were performed using reagentgrade ammonium acetate to simplify the reaction. Later, actual fermentation broth was employed. The primary objective of this study was to provide the optimal operating conditions to make the downstream processing steps of the MixAlco process compatible with ammonium carboxylate salts formed in the fermentation. The optimal initial concentration for reactive extraction should be 150-200 g/L and the volume ratio of aqueous phase and extractant should be 1:1. The distribution coefficient reaches the maximum value when the concentration of TOA is 20% (vol %) in n-octanol. The batch distillation study shows that there are two reaction stages: (1) water leaves the system at 100-106 ?C and (2) the acid-amine complex decomposes at 160-180 ?C.