RESUMEN
The establishment of sulfate (SO42-) reduction during methanogenesis may considerably hinder the efficient energetic exploitation of methane, once removing sulfide from biogas is obligate and can be costly. In addition, sulfide generation can negatively impact the performance of methanogens by triggering substrate competition and sulfide inhibition. This study investigated the impacts of removing SO42- during fermentation on the performance of a second-stage methanogenic continuous reactor (R2), comparing the results with those obtained in a single-stage system (R1) fed with SO42--rich wastewater (SO42- of up to 400 mg L-1, COD/SO42- of 3.12-12.50). The organic load (OL) was progressively increased to 5.0 g COD d-1 in both reactors, showing completely discrepant performances. Sulfate-reducing bacteria outperformed methanogens in the consumption for organic matter during the start-up phase (OL = 2.5 g COD d-1) in R1, directing up to 73% of the electron flow to SO42- reduction. An efficient methanogenic activity was established in R1 only after decreasing the OL to 0.625 g COD d-1, after which methanogenesis prevailed by consuming ca. 90% of the removed COD. Nevertheless, high sulfide proportions (up to 3.1%) were measured in biogas. Conversely, methanogenesis was promptly established in R2, resulting in a methane-rich (> 80%) and sulfide-free biogas regardless of the operating condition. From an economic perspective, processing the biogas evolved from R2 would be cheaper, although the techno-economic impacts of managing the sulfur pollution in the fermentative reactor still need to be understood.
RESUMEN
The establishment of a sulfidogenic environment under thermophilic (55 °C) acidogenic conditions was assessed in an innovative structured-bed bioreactor to enhance sulfate removal and acetate production prior to methanogenesis. Diversified operating strategies, i.e., variations in the hydraulic retention time (HRT; 6-12 h), sulfate loading rate (SLR; 8-16 kg SO42- m-3 day-1) and liquid phase recirculation ratio (0.0-57.0) were assessed to both enable the establishment of sulfate-reducing conditions and remove H2S from the liquid phase. Ethanol was used as the only carbon source. Applying a low HRT (6 h) as the initial operating strategy severely hindered the establishment of sulfate-reducing bacteria (SRB) populations within the system (sulfate removal < 27.5%). In turn, applying effluent recirculation had a positive impact on the system (sulfate removal â¼ 60%) by providing an adequate buffer control along the entire height of the system, as well by displacing over 70% of the H2S to the gaseous phase. The maintenance of pH values above 6.1 proved to be adequate for the sulfidogenic activity, whereas enhanced acidic conditions (pH < 6.0) at the basal portion of the reactor comprised a determining factor to hinder sulfate reduction. SRB were able to handle H2S and acetate concentrations as high as 232 mg L-1 and 3111 mg L-1, respectively, after establishing an effective acidogenic/sulfidogenic environment, indicating that the proposed system has the potential to be used as the first stage in the anaerobic processing of sulfate-rich wastewater streams.
