Many industrial activities generate effluents containing sulfur compounds, both as liquid or gaseous emissions, which are mainly treated through physical-chemical processes. Sulfate is generally present in wastewaters coming from paper, pharmaceutical, mining or food processing industries, among others. As such, sulfate is not a harmful compound, but if it is poured into rivers or sewage systems, an imbalance in the overall sulfur cycle can be generated. Inside this cycle, the last product after the reduction of sulfur compounds is hydrogen sulfide (H2S). This compound is corrosive, odorous and toxic at low concentrations. For these reasons, there is a need to develop environmentally friendly alternatives to valorize not only gaseous emissions, such as SO2 emissions, but also S-rich liquid effluents. In addition, a further recovery of elemental sulfur from these effluents could be obtained providing an opportunity to recover resources in the framework of the circular economy. With these premises, the SONOVA project, in which this thesis is enclosed, is based in the development of a comprehensive treatment process to valorize SOx and NOx from flue gases by economical, robust and environmentally friendly biological methods. It also takes into account the reuse of energy and resources along the process as well as residues valorization. The proposed process is based on a first double stage for selective absorption of SOx and NOx; a second biological step for reducing the sulfate from the first absorption stage to hydrogen sulfide (which is the focus of this thesis); and a third biological stage for the oxidation of hydrogen sulfide to elemental sulfur and its subsequent recovery. Biological-based systems, such as Up-flow Anaerobic Sludge Bed (UASB) reactors, have been developed and implemented world-wide to treat many types of wastewater and to produce biogas through anaerobic digestion. In this thesis, the use of an UASB reactor for the treatment of synthetic wastewater with sulfate was studied, specifically selecting crude glycerol as carbon source and electron donor. Both physical-chemical processes and molecular biology techniques were used to get a broad knowledge of the anaerobic process. The influence of possible inhibitions and competition between sulfate reducers and methanogens was studied in order to improve sulfate removal and sulfide production. It was observed that in long-term operations (after 200 days approximately) methanogens were washed out from the system and sulfate reducers colonized the reactor sludge. However, acetate accumulation was observed because of the disappearance of methanogens, leading to a loss of carbon source in the outlet of the reactor that could have been used to produce sulfide in the UASB. Long-term performances allow detecting further limitations of the system. A loss of granular structure and the growth of unidentified non-sulfate reducer, non-methanogenic biofilm was observed during UASB operations along this thesis. This biofilm, called slime substance along this thesis, was found to be a crucial factor affecting our system, conferring properties such as viscosity to the sludge. Consequently, problems related to mass transfer limitations could be observed, affecting as well, the sulfate reducing activity of the granules and leading to failure operations. Finally, since the accumulation of acetate could not be avoided, experiments were designed to pursue the enrichment of acetate degrading sulfate reducing bacteria in serum bottles, with the final objective of improving sulfidogenesis. In addition, isolation of potential acetate-utilizing sulfate reducers was also pursued. Unfortunately, a culture able to perform sulfate reduction with acetate was not developed during the enrichment experiments. Therefore, further research is needed to enhance the operation in terms of organic matter consumption and sulfide productivity in the long-term.
|Date of Award||22 Sept 2020|
|Supervisor||Maria Isabel Mora Garrido (Director) & David Gabriel Buguña (Director)|