Quoc P. Nguyen

Morphology and Stability of CO2-in-Water Foams with Nonionic Hydrocarbon Surfactants

The morphologies, stabilities, and viscosities of high-pressure carbon dioxide-in-water (C/W) foams (emulsions) formed with branched nonionic hydrocarbon surfactants were investigated by in situ optical microscopy and capillary rheology. Over two dozen hydrocarbon surfactants were shown to stabilize C/W foams with Sauter mean bubble diameters as low as 1 to 2 microm. Coalescence of the C/W foam bubbles was rare for bubbles larger than about 0.5 microm over a 60 h time frame, and Ostwald ripening became very slow. By better blocking of the CO(2) and water phases with branched and double-tailed surfactants, the interfacial tension decreases, the surface pressure increases, and the C/W foams become very stable. For branched surfactants with propylene oxide middle groups, the stabilities were markedly lower for air/water foams and decane-water emulsions. The greater stability of the C/W foams to coalescence may be attributed to a smaller capillary pressure, lower drainage rates, and a sufficient surface pressure and thus limiting surface elasticity, plus small film sizes, to hinder spatial and surface density fluctuations that lead to coalescence. Unexpectedly, the foams were stable even when the surfactant favored the CO(2) phase over the water phase, in violation of Bancrofts rule. This unusual behavior is influenced by the low drainage rate, which makes Marangoni stabilization of less consequence and the strong tendency of emerging holes in the lamella to close as a result of surfactant tail flocculation in CO(2). The high distribution coefficient toward CO(2) versus water is of significant practical interest for mobility control in CO(2) sequestration and enhanced oil recovery by foam formation.

Effect of branching on the interfacial properties of nonionic hydrocarbon surfactants at the air–water and carbon dioxide–water interfaces

The interfacial tensions, surface pressures, and adsorption of nonionic hydrocarbon surfactants at the air-water (A-W) and carbon dioxide-water (C-W) interfaces were investigated systematically as a function of the ethylene oxide (EO) unit length and tail structure. Major differences in the properties are explained in terms of the driving force for surfactant adsorption, tail solvation, area per surfactant molecule, and surfactant packing. As the surfactant architecture is varied, the changes in tail-tail interactions, steric effects, areas occupied by the surfactant at the interface, and tail hydrophobicity are shown to strongly influence the interfacial properties, including the surfactant efficiency (the concentration to produce 20 mN/m interfacial tension reduction). For linear surfactants at the A-W interface, high efficiencies result from dense monolayers produced by the high interfacial tension driving force for adsorption and strong tail-tail interactions. At the C-W interface, where a low interfacial tension leads to a much lower surfactant adsorption, the contact between the phases is much greater. Branching or increasing the number of tail chains increase the hydrophobicity, tail solvation, and adsorption of the surfactant. Furthermore, the area occupied by the surfactant increases with branching, number of tails, and number of EO monomers in the head group, to reduce contact of the phases. These factors produce greater efficiencies for branched and double tail surfactants at the C-W interface, as well as surfactants with longer EO head groups.

Effect of silica nanoparticles on clay swelling and aqueous stability of nanoparticle dispersions

The results of the effects of electrolyte type and concentration, nanoparticle concentration, pH, and temperature on the mobility and aqueous stability of polyethylene glycol (PEG)-coated silica nanoparticles are presented. Nanoparticle mobility was evaluated based on the ability to inhibit montmorillonite swelling in aqueous solutions through visual swelling tests, and the results were quantified in terms of the swelling index. The presence of PEG-coated silica nanoparticles was found to have a positive influence on the inhibition of clay swelling only in the presence of electrolytes. Quantification of nanoparticle stability in the presence of montmorillonite particles was achieved using ultraviolet–visible (UV–vis) spectrophotometry. At the highest concentration of montmorillonite dispersion studied, interaction between the dispersed montmorillonite particles and PEG-coated silica nanoparticles resulted in nanoparticle aggregation as indicated by increased turbidity and absorbance readings. Both nanoparticle concentration and montmorillonite dispersion concentration, in addition to the presence and concentration of NaCl, were found to strongly influence the stability of the mixture.

Modeling Low Salinity Waterflooding: Ion Exchange, Geochemistry and Wettability Alteration

Low salinity waterflood (LSW) has become an attractive enhanced oil recovery (EOR) method as it shows more advantages than conventional chemical EOR methods in terms of chemical costs, environmental impact, and field process implementation. Extensive laboratory studies in the past two decades have proposed several porescale mechanisms of oil displacement during LSW flooding, which are still open for discussion. However, the capability of reservoir simulators to model accurately this process is very limited. This paper provides a critical review of the state of the art in research and field applications of LSW. The focus is on a widely agreed mechanism that is the wettability alteration from preferential oil wetness to water wetness of formation rock surfaces. Ion exchange and geochemical reactions have been experimentally found to be important in oil mobilization due to enhanced water spreading at low salinity. To evaluate the significance of this surface wetting mechanism, a comprehensive ion exchange model with geochemical processes has been developed and coupled to the multi-phase multi-component flow equations in an equation-of-state compositional simulator. This new model captures most of the important physical and chemical phenomena that occur in LSW, including intra-aqueous reactions, mineral dissolution/precipitation, ion exchange and wettability alteration. The proposed LSW model is tested using the low-salinity core-flood experiments reported by Fjelde et al. (2012) for a North Sea reservoir and the low-salinity and high-salinity heterogeneous core-flood experiments by Rivet (2009) for a Texas reservoir. Excellent agreements between the model and the experiments in terms of effluent ion concentrations, effluent pH, and oil recovery were achieved. In addition, the model was also proved to be highly comparable with the ion-exchange model of the geochemistry software PHREEQC for both low salinity and high salinity (Appelo, 1994). Important observations in laboratory and field tests such as local pH increase, decrease in divalent effluent concentration, mineralogy contributions, and the influence of connate water and injected brine compositions can be reproduced with the proposed LSW model. Built in a robust reservoir simulator, it serves as a powerful tool for LSW design and the interpretation of process performance in field tests. Introduction Low salinity waterflooding (LSW) is an emerging EOR technique in which the salinity of the injected water is controlled to improve oil displacement efficiency without a significant loss of infectivity due to clay swelling. In particular, the presence of clay minerals is a favorable condition for the high efficiency of this process. This recovery concept is quite attractive as 50% of the world’s conventional petroleum reservoirs are found in sandstones that commonly contain clay minerals. It has been experimentally found that changes in the injected brine composition can improve waterflood performance by up to 38% (Larger et al. 2004, Web et al. 2004), leading to a new concept of optimal injection brine composition for water flood. In the 1990s, Jadhunandan and Morrow (1995) and Yildiz and Morrow (1996) reported the influence of brine composition on oil recovery, which identified a possibility to improve waterfloods with optimized injection brine formulation. Numerous laboratory experiments (Tang and Morrow, 1997; Morrow

Injection strategies to overcome gravity segregation in simultaneous gas and water injection into homogeneous reservoirs

We extend a model for gravity segregation in steady-state gas/water injection into homogeneous reservoirs for enhanced oil recovery (EOR). A new equation relates the distance gas and water flow together directly to injection pressure, independent of fluid mobilities or injection rate. We consider three additional cases: coinjection of gas and water over only a portion of the formation interval, injection of water above gas over the entire formation interval, and injection of water and gas in separate zones well separated from each other. If gas and water are injected at fixed total volumetric rates, the horizontal distance to the point of complete segregation is the same, whether gas and water are coinjected over all or any portion of the formation interval. At fixed injection pressure, the deepest penetration of mixed gas and water flow is expected when fluids are injected along the entire formation interval. At fixed total injection rate, injection of water above gas gives deeper penetration before complete segregation than does coinjection, but again exactly where the two fluids are injected does not affect the distance to the point of segregation. At fixed injection pressure, injection of water above gas is predicted to give deeper penetration before complete segregation. When injection pressure is limited, the best strategy for simultaneous injection of both phases from a vertical well would be to inject gas at the bottom of the reservoir and water over the rest of the reservoir height, with the ratio of the injection intervals adjusted to maximize overall injectivity. The 2D model applies equally to gas/water flow and to foam, and to injection of water above gas from separate intervals of a vertical well or from two parallel horizontal wells, as long as injection is uniform along each horizontal well. Sample computer simulations for foam injection agree well with the model predictions if numerical dispersion is controlled.

Switchable Nonionic to Cationic Ethoxylated Amine Surfactants for CO2 Enhanced Oil Recovery in High-Temperature, High-Salinity Carbonate Reservoirs

Yunshen Chen, SPE, Amro S. Elhag, and Benjamin M. Poon, Department of Chemical Engineering, University of Texas at Austin; Leyu Cui, and Kun Ma, Department of Chemical and Biomolecular Engineering, Rice University; Sonia Y. Liao, Prathima P. Reddy and Andrew J. Worthen, SPE, Department of Chemical Engineering, University of Texas at Austin; George J. Hirasaki, SPE, Department of Chemical and Biomolecular Engineering, Rice University; Quoc P. Nguyen, SPE, Department of Petroleum and Geosystems Engineering, University of Texas at Austin; Sibani L. Biswal, Department of Chemical and Biomolecular Engineering, Rice University; and Keith P. Johnston, Department of Chemical Engineering, University of Texas at Austin

Aggregation kinetics and shear rheology of aqueous silica suspensions

The kinetics of aggregation of silica nanoparticle solutions as a function of NaCl and silica concentrations is studied experimentally and theoretically. Silica nanoparticles form fractal aggregates due to the collapse of the electrical double layer at high salt concentrations and resulting reduction in stabilizing repulsive force. We propose a convenient model to describe the aggregation of silica nanoparticles and the growth of their aggregate size that depends on particle size and concentration and salt concentration. The model agrees well with experimental data. The aggregation of silica nanoparticles also affects the rheology of the suspension. We propose an equilibrium approach for sediment volume fraction to determine the maximum effective packing fraction. The results for the relative viscosity of silica aggregates agree well with the proposed viscosity model, which also collapses onto a single master curve.

Phase behavior and interfacial properties of a switchable ethoxylated amine surfactant at high temperature and effects on CO2-in-water foams

The interfacial properties for surfactants at the supercritical CO2-water (C-W) interface at temperatures above 80°C have very rarely been reported given limitations in surfactant solubility and chemical stability. These limitations, along with the weak solvent strength of CO2, make it challenging to design surfactants that adsorb at the C-W interface, despite the interest in CO2-in-water (C/W) foams (also referred to as macroemulsions). Herein, we examine the thermodynamic, interfacial and rheological properties of the surfactant C12-14N(EO)2 in systems containing brine and/or supercritical CO2 at elevated temperatures and pressures. Because the surfactant is switchable from the nonionic state to the protonated cationic state as the pH is lowered over a wide range in temperature, it is readily soluble in brine in the cationic state below pH 5.5, even up to 120°C, and also in supercritical CO2 in the nonionic state. As a consequence of the affinity for both phases, the surfactant adsorption at the CO2-water interface was high, with an area of 207Å(2)/molecule. Remarkably, the surfactant lowered the interfacial tension (IFT) down to ∼5mN/m at 120°C and 3400 psia (23MPa), despite the low CO2 density of 0.48g/ml, indicating sufficient solvation of the surfactant tails. The phase behavior and interfacial properties of the surfactant in the cationic form were favorable for the formation and stabilization of bulk C/W foam at high temperature and high salinity. Additionally, in a 1.2 Darcy glass bead pack at 120°C, a very high foam apparent viscosity of 146 cP was observed at low interstitial velocities given the low degree of shear thinning. For a calcium carbonate pack, C/W foam was formed upon addition of Ca(2+) and Mg(2+) in the feed brine to keep the pH below 4, by the common ion effect, in order to sufficiently protonate the surfactant. The ability to form C/W foams at high temperatures is of interest for a variety of applications in chemical synthesis, separations, materials science, and subsurface energy production.

Interface tension of silica hydroxylated nanoparticle with brine: A combined experimental and molecular dynamics study

We have used molecular dynamics simulations to calculate the interfacial tension of hydroxylated SiO(2) nanoparticles under different temperatures and solutions (helium and brine with monovalent and divalent salts). In order to benchmark the atomistic model, quartz SiO(2) interfacial tension was measured based on inverse gas chromatography under He atmosphere. The experimental interfacial tension values for quartz were found between 0.512 and 0.617 N/m. Our calculated results for the interfacial tension of silica nanoparticles within helium atmosphere was 0.676 N/m, which is higher than the value found for the system containing He∕α-quartz (0.478 N/m), but it is similar to the one found for amorphous silica surface. We have also studied the interfacial tension of the nanoparticles in electrolyte aqueous solution for different types and salts concentrations (NaCl, CaCl(2), and MgCl(2)). Our calculations indicate that adsorption properties and salt solutions greatly influence the interfacial tension in an order of CaCl(2) > MgCl(2) > NaCl. This effect is due to the difference in distribution of ions in solution, which modifies the hydration and electrostatic potential of those ions near the nanoparticle.

Phase behavior and rheological characterization of silica nanoparticle gel

Preferential injection into high permeability thief zones or fractures can result in early breakthrough at production wells and large unswept areas of high oil saturation, which impact the economic life of a well. A variety of conformance control techniques, including polymer and silica gel treatments, have been designed to block flow through the swept zones. Over a certain range of salinities, silica nanoparticle suspensions form a gel in bulk phase behavior tests. These gels have potential for in situ flow diversion, but in situ flow tests are required to determine their applicability. To determine the appropriate scope of the in situ tests, it is necessary to obtain an accurate description of nanoparticle phase behavior and gel rheology. In this paper, the equilibrium phase behavior of silica nanoparticle solutions in the presence of sodium chloride (NaCl) is presented with four phase regions classified as a function of salinity and nanoparticle concentration. Once the gelation window was clearly defined, rheology experiments of silica nanoparticle gels were also carried out. Gelation time decreases exponentially as a function of silica concentration, salinity, and temperature. Following a power law behavior, the storage modulus, G′, increases with particle concentration. Steady shear measurements show that silica nanoparticle gels exhibit non-Newtonian, shear thinning behavior. This comprehensive study of the silica nanoparticle gels has provided a clear path forward for in situ tests to determine the gel’s applicability for conformance control operations.