Influence of operating conditions on sulfate reduction from real mining process water by membrane biofilm reactors

Two H₂-based membrane biofilm reactor (H₂-MBfR) systems, differing in membrane type, were tested for sulfate reduction from a real mining-process water having low alkalinity and high concentrations of dissolved sulfate and calcium. Maximum sulfate reductions were 99%, with an optimum pH range between 8 and 8.5, which minimized any toxic effect of unionized hydrogen sulfide (H₂S) on sulfate-reducing bacteria (SRB) and calcite scaling on the fibers and in the biofilm. Although several strategies for control of pH and gas back-diffusion were applied, it was not possible to sustain a high degree of sulfate reduction over the long-term. The most likely cause was precipitation of calcite inside the biofilm and on the surface of fibers, which was shown by scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) analysis. Another possible cause was a decline in pH, leading to inhibition by H₂S. A H₂/CO₂ mixture in the gas supply was able to temporarily recover the effectiveness of the reactors and stabilize the pH. Biomolecular analysis showed that the biofilm was comprised of 15–20% SRB, but a great variety of autotrophic and heterotrophic genera, including sulfur-oxidizing bacteria, were present. Results also suggest that the MBfR system can be optimized by improving H₂ mass transfer using fibers of higher gas permeability and by feeding a H₂/CO₂ mixture that is automatically adjusted for pH control.