Inhibition of microbial souring with molybdate and its application under reservoir conditions

Souring induced by sulfate reducing microorganisms (SRM) represents a severe problem in the petroleum industry. In addition to conventional biocides and nitrate, alternative SRM inhibitors such as molybdate have been proposed recently for controlling microbial souring. We used oilfield-derived microbial consortia, rock and fluids to test molybdate as a specific SRM inhibitor for a microbial enhanced oil recovery (MEOR) application where souring might occur as a side effect. SRM cells were quantified and dissolved molybdate, sulfate and gaseous hydrogen sulfide were measured under different dynamic conditions in sandpacks with and without residual oil. In batch experiments, 0.5 mM molybdate inhibited SRM growth whereas hydrogen sulfide and mineral precipitations were observed in bottles amended with 100 mM nitrate. However, significant molybdate adsorption onto reservoir rock occurred and maximum Langmuir saturation was estimated to be ≥ 34 μmol g⁻¹. Residual oil allowed a further propagation of molybdate into sandpacks, but a pH < 6 and sulfide concentrations >11 μMH₂S ₐq limited the efficiency of molybdate due to rapid adsorption. Under favorable souring conditions, we also observed the localized formation of macroscopic iron sulfide precipitations. These resulted in a four-fold permeability decrease after the injection of SRM substrates for 40 days and a calculated mean sulfate reduction rate of 52 μM h⁻¹. However, delayed sulfate reduction in molybdate-preflushed sandpacks suggests an inhibitory effect even if molybdate is partially adsorbed. Sulfate reduction was not detected when molybdate was continuously injected with MEOR nutrients into sandpacks demonstrating its inhibitory efficiency in case it is applied in early phases of field operations with a potential risk of souring.