Thermodynamic method for analyzing and optimizing pretreatment/anaerobic digestion systems

This paper builds a quantitative thermodynamic model for the microbial hydrolysis process (MHP, which uses Caldicellulosiruptor bescii at 75°C for pre-digestion) for producing biogas from a 5-10% aqueous suspension of dairy manure (naturally buffered near pH 7.8 by ammonium bicarbonate) by anaerobic digestion with a mix of acetoclastic and syntrophic methanogenesis. Standard Gibbs energy changes were calculated for the major reactions in pre-digestion, for reactions producing H2, acetate, and CO2 in the digester, and for methanogenesis reactions in the digester. The available data limit the study to analyzing reactions in the digester to reactions of short-chain volatile fatty acids anions. Results are presented as curves of ΔrxnG (Gibbs energy change) vs. acetate concentration. The H2(aq) concentration must be above 1.2×10-9 M to get significant syntrophic methanogenesis, i.e., for ΔrxnG to be negative. The results show syntrophic methanogenesis of propionate, butyrate, and valerate slows as acetate concentration increases because hydrogen production also decreases, and consequently, biogas production from syntrophic methanogenesis slows as acetate increases. Bicarbonate also inhibits both acetoclastic and syntrophic methanogenesis but is necessary to prevent acidification (souring) of the digester. At identical steady-state conditions, acetoclastic methanogenesis runs about 1.4 times faster than syntrophic methanogenesis. Because syntrophic methanogenesis produces acetate catabolized by acetoclastic methanogens, both types of methanogens are necessary to maximize biogas production. The culture in the digester is predicted to evolve to optimize the ratio of acetoclastic methanogens to syntrophic methanogens, a condition signaled by a constant, low acetate concentration in the digester effluent. Obtaining volatile solids reduction as high as 75% with MHP requires a feedstock with less than 25% lignin and a culture of acetoclastic methanogens and syntrophic methanogens and their symbiotic bacteria.