Chemical Compositions in Modified Salinity Waterflooding of Calcium Carbonate Reservoirs: Experiment

Modified or low-salinity waterflooding of carbonate oil reservoirs is of considerable economic interest because of potentially inexpensive incremental oil production. The injected modified brine changes the surface chemistry of the carbonate rock and crude oil interfaces and detaches some of adhered crude oil. Composition design of brine modified to enhance oil recovery is determined by labor-intensive trial-and-error laboratory corefloods. Unfortunately, limestone, which predominantly consists of aqueous-reactive calcium carbonate, alters injected brine composition by mineral dissolution/precipitation. Accordingly, the rock reactivity hinders rational design of brines tailored to improve oil recovery. Previously, we presented a theoretical analysis of 1D, single-phase brine injection into calcium carbonate-rock that accounts for mineral dissolution, ion exchange, and dispersion (Yutkin et al. in SPE J 23(01):084–101, 2018. 10.2118/182829-PA). Here, we present the results of single-phase waterflood-brine experiments that verify the theoretical framework. We show that concentration histories eluted from Indiana limestone cores possess features characteristic of fast calcium carbonate dissolution, 2:1 ion exchange, and high dispersion. The injected brine reaches chemical equilibrium inside the porous rock even at injection rates higher than 3.5 $$\times$$ × 10$$^{-3}$$ - 3 m s$$^{-1}$$ - 1 (1000 ft/day). Ion exchange results in salinity waves observed experimentally, while high dispersion is responsible for long concentration history tails. Using the verified theoretical framework, we briefly explore how these processes modify aqueous-phase composition during the injection of designer brines into a calcium-carbonate reservoir. Because of high salinity of the initial and injected brines, ion exchange affects injected concentrations only in high surface area carbonates/limestones, such as chalks. Calcium-carbonate dissolution only affects aqueous solution pH. The rock surface composition is affected by all processes.

Aragonite is calcite’s best friend at the seafloor

In the open ocean, calcium carbonates are mainly found in two mineral forms. Calcite, the least soluble, is widespread at the seafloor, while aragonite, the more soluble, is rarely preserved in marine sediments. Despite its greater solubility, research has shown that aragonite, which could contribute between 10 and 90% to pelagic calcium carbonate production, is able to reach the deep-ocean. If large quantities of aragonite settle and dissolve at the seafloor, this represents a large source of alkalinity that buffers the deep ocean and favours the preservation of less soluble calcite, acting as a deep-sea, carbonate version of galvanization. Here, we investigate the role of aragonite dissolution on the early diagenesis of calcite-rich sediments using a novel 3D, micrometric-scale reactive-transport model combined with 3D, X-ray tomography structures of natural aragonite and calcite shells. Results highlight the important role of diffusive transport in benthic calcium carbonate dissolution, in agreement with recent work. We show that, locally, aragonite fluxes to the seafloor could be sufficient to suppress calcite dissolution in the top layer of the seabed, possibly causing calcite recrystallization. As aragonite producers are particularly vulnerable to ocean acidification, the proposed galvanizing effect of aragonite could be weakened in the future, indirectly boosting calcite dissolution further.

Novel Cake Washer for Removing Oil-Based Calcium Carbonate Filter Cake in Horizontal Wells

An impermeable layer “filter cake” usually forms during the overbalanced drilling technique. Even though it helps in protecting the formation from a further invasion of drilling fluids, the removal of this layer is essential for a proper cement job and to avoid any reduction in wellbore deliverability. The design of the removal process is complicated and depends on the filter cake composition and homogeneity. This paper presents an experimental evaluation on the usage of a novel cake washer (NCW) in the removal of a filter cake formed by an invert emulsion oil-based drilling fluid that contains calcium carbonate as a weighting material while drilling a horizontal reservoir. The proposed NCW is a mixture of organic acid, mutual solvent and nonionic surfactant. It is designed to enable restored wellbore permeability for a sustainable production. Since the filter cake mainly consists of the weighting material, the solubility of calcium carbonate in NCW at different ranges of temperature, duration and concentration was investigated. An actual casing joint was used to test the corrosion possibility of the treating solution. High-pressure and high-temperature (HPHT) filtration tests on ceramic discs and Berea sandstone core samples were conducted to measure the efficiency of the filter cake removal and the retained permeability. Ethylene glycol mono butyl ether (EGMBE) was used as a mutual solvent and the solubility was higher compared to when the mutual solvent was not used in the washer formulation. A significant increase in calcium carbonate dissolution with time was observed for a duration of 24 h. The solubility was found to be proportional to the concentration of NCW with optimum results of 99% removal at a temperature of around 212 °F. At those conditions, no major corrosion problems were detected. Permeability of the core retained its pristine value after the treatment.