Extended Downhole Protection by Preservative Biocides as Demonstrated in High Pressure, High Temperature Bioreactors

Preservative biocides are designed to control microbial growth and biogenic souring in the downhole environment. We report the prevention of biogenic souring by 4,4-dimethyloxazolidine (DMO, a preservative biocide) and glutaraldehyde as compared to that afforded by tributyl tetradecyl phosphonium chloride (TTPC, a cationic surface-active biocide), in a first-of-its kind suite of High Pressure, High Temperature (HPHT) Bioreactors that simulate hydraulically fractured shale reservoirs. The design of these new bioreactors, which recreate the downhole environment (temperatures, pressures, formation solids, and frac additives) in a controlled laboratory environment, enables the evaluation of biocides under field-relevant conditions. The bioreactors receiving either no biocide treatment or treatment with a high concentration of TTPC (50 ppm active ingredient) rapidly soured within the first two weeks of shut-in, and all surpassed the maximum detectable level of H2S (343 ppm) after the addition of live microbes to the reactors. Conversely, a higher loading of DMO (150 pppm active ingredient) maintained H2S concentrations below the minimum dectable level (5 ppm) for six weeks, and held H2S concentrations to 10.3 +/- 5.2 ppm after fifteen weeks of shut-in and two post shut-in microbial rechallenges. In a second study, a lower concentration of DMO (50 ppm active ingredient) maintained H2S concentrations below the minimum detectable level through the addition of live microbes after three weeks, and H2S concentrations only registered above 10 ppm upon a second addition of live microbes after five weeks. In this same study (which was performed at moderate temperatures), a 50 ppm (active ingredient) treatment of glutaraldehyde also maintained H2S concentrations below the minimum detectable level through the addition of live microbes after three weeks, and H2S concentrations registered 15.0 +/- 9.7 ppm H2S after four weeks. Similar time scales of protection are observed for each treatment condition through the enumeration of microbes present in each reactor. The differentiation in antimicrobial activity (and specifically, prevention of biogenic souring) afforded by DMO and glutaraldehyde suggests that such nonionic, preservative biocides are a superior choice for maintaining control over problematic microorganisms as compared to surface-active biocides like TTPC at the concentrations tested. The significant duration of efficacy provided by DMO and glutaraldehyde in this first-of-its-kind suite of simulated reservoirs demonstrates that comprehensive preservation and prevention of biogenic souring from completion through to production is feasible. Such comprehensive, prolonged protection is especially relevant for extended shut-ins or drilled but uncompleted wells (DUCS) such as those experienced during the COVID-19 pandemic. The environment simulated within the bioreactors demonstrates that the compatibility afforded by a preservative biocide offers downhole protection that cationic, surface-active biocides do not.