Flow-Through Experiments of Reactive Ba-Sr-Mg Brines in Mons Chalk at North Sea Reservoir Temperature at Different Injection Rates
Authors: Andersen Pål Østebø , Herlofsen Sander Sunde , Korsnes Reidar Inge , Minde Mona Wetrhus 
Published: August 2023

Summary
North Sea Chalk reservoirs in Norway are potential candidates for enhanced hydrocarbon recovery by modifying the injected brine composition. This work investigates how barium (Ba), strontium (Sr), and magnesium (Mg) brines interact when injected into chalk. Ba and Sr are often associated with mineral precipitation and occur in formation water, while Mg is present in seawater, commonly injected in chalk.
Relatively clean (&gt;99% calcite) outcrop chalk cores from Mons, Belgium, were flooded at 130°C in triaxial cells with four brines containing 0.12 mol/L divalent cations, either 0.06 mol/L Sr and Ba, 0.06 mol/L Sr and Mg, or 0.12 mol/L Ba or Sr. Each brine was injected in a separate core, with 100–150 pore volumes (PV). The injection rate varied between 0.5 and 8 PV/D. Produced brine was analyzed continuously and compared with the injected composition. After flooding, the cores flooded with only Ba or only Sr were cut into slices and analyzed locally in terms of scanning electron microscopy (SEM), matrix density, specific surface area (SSA), and X-ray diffraction (XRD).
In all experiments, the produced divalent cation concentration was reduced compared with the injected value. The total reduction of injected cation concentration closely equaled the produced Ca concentration (from calcite dissolution). When flooding 0.12 mol/L Sr, the Sr concentration depleted 55%, while when flooding 0.12 mol/L Ba, 15% Ba depleted. When injecting equal concentrations of Ba and Sr, 40% Sr and 7% Ba depleted, while with equal concentrations of Mg and Sr injected, ~50% Sr was retained and almost no Mg depleted. Sr appeared to dominate and suppress other reactions. There was less sensitivity in steady-state concentrations with variation in injection rate. The similar modification of the brine regardless of residence time suggests the reactions reached equilibrium.
Cutting the cores revealed a visually clear front a few centimeters from the inlet. The material past the front was indistinguishable from unflooded chalk in terms of density, SSA, microscale structure, porosity, and composition [XRD and SEM-energy-dispersive spectroscopy (EDS)]. The material near the inlet was clearly altered. Images, XRD, SEM-EDS, and geochemical simulations indicated that BaCO3 and SrCO3 formed during BaCl2 and SrCl2 flooding, respectively. Geochemical simulations also predicted an equal exchange of cations to occur. The matrix densities, porosities, and the distance traveled by the front corresponded with these minerals and suggested that the chalk was completely converted to these minerals behind the front.
It was demonstrated that Ba, Sr, and Mg brines and their mixtures can be highly reactive in chalk without clogging the core, even after 100 + PV. This is because the precipitation of minerals bearing these ions is associated with simultaneous dissolution of calcite. The Ca-, Ba-, and Sr-mineral reactions are effectively in equilibrium. Previous investigations with MgCl2 (in pure and less pure chalk, at 130°C) show injection rate-dependent results (Andersen et al. 2022) and smoother alterations [Mg precipitation was seen from inlet to outlet (Zimmerman et al. 2015)], indicating that Mg-mineral reactions at same conditions have a longer time scale. The limited distance mineral alteration has occurred, suggesting that adsorption processes, happening in parallel, can explain previous observations (Korsnes and Madland 2017) of Ba and Sr injection strengthening chalk. Flushing out formation water with these ions during injection may be a new water-weakening mechanism.