SmartWater flooding through injection of chemistry optimized waters by tuning individual ions is recently getting more attention in the industry for improved oil recovery in carbonate reservoirs. Most of the research studies described so far in this area have been limited to studying the interactions at rock-fluids interfaces by measuring contact angles, zeta potential, and adhesion forces. The other widely reported interfacial tension data at oil-water interfaces do not consider the formation of interfacial monolayer and the interfacial tension is estimated as an average parameter relying on the properties of two individual bulk phases. As a result, such measurements have serious shortcomings to provide any details on complex microscopic scale interactions occurring directly at the interface between crude oil and water to understand the SmartWater flood recovery mechanism.
In this study, two novel interfacial instruments of interfacial shear rheometer and surface potential sensor were used to study microscopic scale interactions of various individual water ions at both air-water and complex crude oil-water interfaces. The measured interfacial rheology data indicated totally different interfacial behavior at crude oil-water interface when compared to air-water interface due to presence of crude oil functional groups. Viscous dominated response was observed at crude oil-water interface for all brine compositions. These interfaces behaved like a viscous fluid without exhibiting viscoelastic solid like properties. Lower interfacial viscous modulus was observed for certain key ions such as calcium, magnesium, and sodium. The interfacial viscous modulus was found to be substantially much higher for sulfates, besides exhibiting some elasticity. The surface potential was gradually decreased by replacing seawater with calcium only brine. The better surface activity with seawater can be attributed to adsorption of more key water ions at the surface.
The interesting results observed with certain water ions at fluid-fluid interfaces are expected to work in tandem with rock-fluids interactions to impact oil recovery in SmartWater flood. At first, they play a role to control the accessibility of active water ions to approach the rock surface, interact with it and subsequently alter wettability. Next oil droplets adhering to the rock surface will be detached and released due to favorable interactions occurring at rock-fluids interfaces. The interfacial film between oil and water can then quickly be destabilized due to less viscous interfaces observed with certain ions to promote drop-drop coalescence and easy mobilization of released oil droplets. This coalescence process is sequential and it would continue until the formation of small oil bank.
This is the first study that showed added importance of fluid-fluid interactions in SmartWater flood by using direct measurements on individual water ions at crude oil-water interface. In addition, a new oil recovery mechanism was proposed by combining both the interactions occurring at fluid-fluid and rock-fluids interfaces. The new fundamental knowledge gained in this study will provide an important guidance on how to synergize water ion interactions at fluid-fluid interfaces with those at rock-fluids interfaces to optimize oil recovery from SmartWater flood.
Low-salinity waterflooding has been portrayed as an effective enhanced-oil recovery technology. Despite compelling laboratory and field evidence of its potential, the underlying mechanisms still remain controversial. In this study, the enhanced-oil recovery mechanisms are investigated considering a distinct interfacial effect, i.e. water-crude oil interfacial viscoelasticity, through analysis of capillary hysteresis. An experimental setup with an oil-wet and a water-wet media on each end face of the core sample was utilized to capture capillary and rock electrical properties hysteresis. Moreover, new improvements over the traditional quasi-static porous plate method were implemented to accelerate measurements. Two experiments were conducted on Minnelusa formation rock samples and TC crude oil, at low temperature (30 °C) and without any significant aging as to minimize wettability alteration. Two core plugs were flooded with high-salinity and low-salinity brines, separately. It is found that the dynamic-static method with a ceramic disk, i.e. a combination of continuous injection in drainage and stepwise quasi-static method in imbibition on short 1" long core samples, allows one to capture the correct envelopes of the capillary pressure curves and save ~ 30% of the total time; a thin membrane is anticipated to save ~90% with respect to traditional quasi-static porous plate method. The capillary hysteresis experiments at low temperature prove that low-salinity brine is able to suppress capillary hysteresis. This is attributed to the formation of a more visco-elastic brine-crude oil interface upon exposure to low-salinity brine, leading to a more continuous oil phase. In addition, we show that wettability plays an essential role on electrical resistivity and the more oil-wet, the more hysteresis occurs, namely that resistivity values in imbibition are higher than those in drainage. The findings in this paper demonstrate that low-salinity waterflooding can still increase oil recovery even in the absence of wettability alteration.
XU, Ke (The University of Texas at Austin) | Zhu, Peixi (The University of Texas at Austin) | Tatiana, Colon (Polytechnic University of Puerto Rico) | Huh, Chun (The University of Texas at Austin) | Balhoff, Matthew (The University of Texas at Austin)
Injecting oil-in-water (O/W) emulsions stabilized with nanoparticles or surfactants is a promising option for enhanced oil recovery (EOR) in harsh-condition reservoirs. Stability and rheology of flowing emulsion in porous media are key factors for the effectiveness of the EOR method. The objective of this study is to use microfluidics to (1) quantitatively evaluate the synergistic effect of surfactants and nanoparticles on emulsion's dynamic stability and how nanoparticles affects the emulsion properties, and (2) investigate how emulsion properties affect the sweep performance in emulsion flooding.
A microfluidic device with well-defined channel geometry of a high-permeability pathway and multiple parallel low-permeability pathways was created to represent a fracture – matrix dual-permeability system. Measurement of droplets’ coalescence frequency during flow is used to quantify the dynamic stability of emulsions. A nanoparticle aqueous suspension (2 wt%) shows excellent ability to stabilize macro-emulsion when mixed with trace amount of surfactant (0.05 wt%), revealing a synergic effect between nanoparticles and surfactant.
For a stable emulsion, it was observed that flowing emulsion droplets compress each other and then block the high-permeability pathway at a throat structure, which forces the wetting phase into low-permeability pathways. Droplet size shows little correlation with this blocking effect. Water content was observed much higher in the low-permeability pathways than in the high-permeability pathway, indicating different emulsion texture and viscosity in channels of different sizes. Consequently, the assumption of bulk emulsion viscosity in the porous medium is not applicable in the description and modeling of emulsion flooding process.
Flow of emulsions stabilized by the nanoparticle-surfactant synergy shows droplet packing mode different from those stabilized by surfactant only at high local oil saturation region, which is attributed to the interaction among nanoparticles in the thin liquid film between neighboring oil-water interfaces. This effect is believed to be an important contributing mechanism for sweep efficiency attainable from nanoparticle-stabilized emulsion EOR process.
Kim, Ijung (Department of Petroleum and Geosystems Engineering, The University of Texas at Austin) | Worthen, Andrew J. (McKetta Department of Chemical Engineering, The University of Texas at Austin) | Lotfollahi, Mohammad (Department of Petroleum and Geosystems Engineering, The University of Texas at Austin) | Johnston, Keith P. (McKetta Department of Chemical Engineering, The University of Texas at Austin) | DiCarlo, David A. (Department of Petroleum and Geosystems Engineering, The University of Texas at Austin) | Huh, Chun (Department of Petroleum and Geosystems Engineering, The University of Texas at Austin)
The immense nanotechnology advances in other industries provided opportunities to rapidly develop various applications of nanoparticles in the oil and gas industry. In particular, nanoparticle has shown its capability to improve the emulsion stability by generating so-called Pickering emulsion, which is expected to improve EOR processes with better conformance control. Recent studies showed a significant synergy between nanoparticles and very low concentration of surfactant, in generating highly stable emulsions. This study's focus is to exploit the synergy's benefit in employing such emulsions for improved mobility control, especially under high-salinity conditions.
Hydrophilic silica nanoparticles were employed to quantify the synergy of nanoparticle and surfactant in oil-in-brine emulsion formation. The nanoparticle and/or the selected surfactant in aqueous phase and decane were co-injected into a sandpack column to generate oil-in-brine emulsions. Four different surfactants (cationic, nonionic, zwitterionic, and anionic) were examined, and the emulsion stability was analyzed using microscope and rheometer.
Strong and stable emulsions were successfully generated in the combinations of either cationic or nonionic surfactant with nanoparticles, while the nanoparticles and the surfactant by themselves were unable to generate stable emulsions. The synergy was most significant with the cationic surfactant, while the anionic surfactant was least effective, indicating the electrostatic interactions with surfactant and liquid/liquid interface as a decisive factor. With the zwitterionic surfactant, the synergy effect was not as great as the cationic surfactant. The synergy was greater with the nonionic surfactant than the zwitterionic surfactant, implying that the surfactant adsorption at oil-brine interface can be increased by hydrogen bonding between surfactant and nanoparticle when the electrostatic repulsion is no longer effective.
In generating highly stable emulsions for improved control for adverse-mobility waterflooding in harsh-condition reservoirs, we show a procedure to find the optimum choice of surfactant and its concentration to effectively and efficiently generate the nanoparticle-stabilized emulsion exploiting their synergy. The findings in this study propose a way to maximize the beneficial use of nanoparticle-stabilized emulsions for EOR at minimum cost for nanoparticle and surfactant.