Willem-Bart Bartels

Kinetics of Low-Salinity-Flooding Effect

Low-salinity waterflooding (LSF) is one of the least-understood enhanced-oil-recovery (EOR)/improved-oil-recovery (IOR) methods, and proper understanding of the mechanism(s) leading to oil recovery in this process is needed. However, the intrinsic complexity of the process makes fundamental understanding of the underlying mechanism(s) and the interpretation of laboratory experiments difficult. Therefore, we use a model system for sandstone rock of reduced complexity that consists of clay minerals (Na-montmorillonite) deposited on a glass substrate and covered with crude-oil droplets and in which different effects can be separated to increase our fundamental understanding. We focus particularly on the kinetics of oil detachment when exposed to lowsalinity (LS) brine. The system is equilibrated first under high-salinity (HS) brine and then exposed to brines of varying (lower) salinity while the shape of the oil droplets is continuously monitored at high resolution, allowing for a detailed analysis of the contact angle and the contact area as a function of time. It is observed that the contact angle and contact area of oil with the substrate reach a stable equilibrium at HS brine and show a clear response to the LS brine toward less-oil-wetting conditions and ultimately detachment from the clay substrate. This behavior is characterized by the motion of the three-phase (oil/water/solid) contact line that is initially pinned by clay particles at HS conditions, and pinning decreases upon exposure to LS brine. This leads to a decrease in contact area and contact angle that indicates wettability alteration toward a more-waterwet state. When the contact angle reaches a critical value at approximately 40 to 50 , oil starts to detach from the clay. During detachment, most of the oil is released, but in some cases a small amount of oil residue is left behind on the clay substrate. Our results for different salinity levels indicate that the kinetics of this wettability change correlates with a simple buoyancyover adhesion-force balance and has a time constant of hours to days (i.e., it takes longer than commonly assumed). The unexpectedly long time constant, longer than expected by diffusion alone, is compatible with an electrokinetic ion-transport model (Nernst-Planck equation) in the thin water film between oil and clay. Alternatively, one could explain the observations only by more-specific [nonDerjaguin–Landau–Verwey–Overbeek (DLVO) type] interactions between oil and clay such as cation-bridging, direct chemical bonds, or acid/base effects that tend to pin the contact line. The findings provide new insights into the (sub) pore-scale mechanism of LSF, and one can use them as the basis for upscaling to, for example, pore-network scale and higher scales (e.g., core scale) to assess the impact of the slow kinetics on the time scale of an LSF response on macroscopic scales.

Driving Mechanism of Low Salinity Flooding in Carbonate Rocks

Several studies conducted mainly on the laboratory scale indicate that in carbonate rocks oil displacement can be influenced by the ionic composition of the brine, providing an opportunity to improve recovery by optimizing the brine mixture used in secondary or tertiary recovery. In industry this topic has been termed “low salinity flooding (LSF) in carbonates” while the underlying mechanisms are not very well understood. The increased oil recovery has been attributed to wettability alteration to a more water-wet state. However, in some studies a positive low salinity effect (LSE) has been ascribed to dissolution of rock, which occurs on the laboratory scale but due to equilibration of brine with carbonate minerals on larger length scales this is not relevant for the reservoir scale. Therefore, the objective of this paper is to gain a better understanding of the underlying mechanism(s) and investigate whether calcite dissolution is the primary mechanism of the LSE. We used a model system where the contact angle of crude oil deposited on planar surfaces coated with crushed carbonate rock particles was monitored as a function of brine composition. The approach is similar to the one published in Mahani et al. (2014) for sandstone rock, but instead of clay minerals we used carbonate materials from natural limestone and Silurian dolomite rocks. Furthermore, the effective surface charge at the oil-water and water-rock interfaces was quantified via zeta-potential measurements at several salinity and pH levels in order to establish a link between changes in the intermolecular interactions at the solid-liquid interface and the contact angle at the brine-oil-rock contact line, which is an indicator for wettability change. The impact of mineral dissolution was addressed by comparing the response to brines that were fully equilibrated (and hence dissolution suppressed) and the response to those completely under-saturated with calcium carbonate (leading to dissolution). The investigation was accompanied by geochemical modeling using PHREEQC. It was observed that by switching from formation water (FW) to seawater (SW), diluted seawater (dSW) and diluted seawater equilibrated with calcite (dSWEQ), the limestone surface became less oil-wet reflected in contact angle decrease. The recession of the 3-phase contact line observed for both SW and dSWEQ, which are not impacted by dissolution, suggests that the LSE occurs even in the absence of mineral dissolution. The trends observed for the zeta-potential data on brine composition clearly support the surface-charge-change mechanism for limestone, where at lower salinities the charges at the limestone-brine interface become more negative, causing lower adhesion or even repulsion between oil and rock. Dolomite rock shows a different behavior. First, there is a much smaller response in terms of contact angle change. Also, the zeta-potential of dolomite shows generally more positive charges at higher salinities and less decrease at lower salinities, where in comparison to limestone the electrostatic interaction remains attractive or becomes only weakly repulsive. In summary we conclude that a positive LSE in carbonate rock exists without any dissolution and it is driven by the brine composition dependency of electrostatic interactions between crude oil and rock. However, the magnitude of the LSE is impacted by the mineralogy of carbonate material.

Pore-scale processes in Amott spontaneous imbibition tests

We observed the redistribution of the oil phase in the pore space of the rock in real-time in water-wet and mixed-wet (by ageing in crude oil) carbonate samples. During the imbibition of the water phase both, pore filling events with connection to the surrounding brine as well as snap-off events connected through water films only were detected. The distribution of the oil in different pore sizes as well as the different event types help to identify the wettability state of the system and understand how pore scale processes lead to the oil production at the larger scale.