Magnetic nanoparticles that can be transported in subsurface reservoirs at high salinities and temperatures are expected to have a major impact on enhanced oil recovery, carbon dioxide sequestration, and electromagnetic imaging. Herein we report a rare example of steric stabilization of iron oxide (IO) nanoparticles (NPs) grafted with poly(2-acrylamido-2-methylpropanesulfonate-co-acrylic acid) (poly(AMPS-co-AA)) that not only display colloidal stability in standard American Petroleum Institute (API) brine (8% NaCl + 2% CaCl2 by weight) at 90 °C for 1 month but also resist undesirable adsorption on silica surfaces (0.4% monolayer NPs). Because the AMPS groups interacted weakly with Ca(2+), they were sufficiently well solvated to provide steric stabilization. The PAA groups, in contrast, enabled covalent grafting of the poly(AMPS-co-AA) chains to amine-functionalized IO NPs via formation of amide bonds and prevented polymer desorption even after a 40,000-fold dilution. The aforementioned methodology may be readily adapted to stabilize a variety of other functional inorganic and organic NPs at high salinities and temperatures.

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To improve sweep efficiency for carbon dioxide (CO 2 ) enhanced oil recovery (EOR) up to 120 C in the presence of high-salinity brine (182 g/L NaCl), novel CO 2 /water (C/W) foams have been formed with surfactants composed of ethoxylated amine headgroups with cocoalkyl tails. These surfactants are switchable from the nonionic (unprotonated amine) state in dry CO 2 to cationic (protonated amine) in the presence of an aqueous phase with a pH less than 6. The high hydrophilicity in the protonated cationic state was evident in the high cloudpoint temperature up to 120 C. The high cloud point facilitated the stabilization of lamellae between bubbles in CO 2 /water foams. In the nonionic form, the surfactant was soluble in CO 2 at 120 C and 3,300 psia at a concentration of 0.2% (w/w). C/W foams were produced by injecting the surfactant into either the CO 2 phase or the brine phase, which indicated good contact between phases for transport of surfactant to the interface. Solubility of the surfactant in CO 2 and a favorable C/W partition coefficient are beneficial for transport of surfactant with CO 2 -flow pathways in the reservoir to minimize viscous fingering and gravity override. The ethoxylated cocoamine with two ethylene oxide (EO) groups was shown to stabilize C/W foams in a 30-darcy sandpack with NaCl concentrations up to 182 g/L at 120 C and 3,400 psia, and foam qualities from 50 to 95%. The foam produces an apparent viscosity of 6.2 cp in the sandpack and 6.3 cp in a 762-lm-inner-diameter capillary tube (downstream of the sandpack) in contrast with values well below 1 cp without surfactant present. Moreover, the cationic headgroup reduces the adsorption of ethoxylated alkyl amines on calcite, which is also positively charged in the presence of CO 2 dissolved in brine. The surfactant partition coefficients (0 to 0.04) favored the water phase over the oil phase, which is beneficial for minimizing losses of surfactant to the oil phase for efficient surfactant usage. Furthermore, the surfactant was used to form C/W foams, without forming stable/viscous oil/water (O/W) emulsions. This selectivity is desirable for mobility control whereby CO 2 will have low mobility in regions in which oil is not present and high contact with oil at the displacement front. In summary, the switchable ethoxylated alkyl amine surfactants provide both high cloudpoints in brine and high interfacial activities of ionic surfactants in water for foam generation, as well as significant solubilities in CO 2 in the nonionic dry state for surfactant injection.

Whereas numerous studies of stabilization of nanoparticles (NPs) in electrolytes have examined biological fluids, the interest has grown recently in media with much higher ionic strengths including seawater and brines relevant to environmental science and subsurface oil and gas reservoirs. Given that electrostatic repulsion is limited at extremely high ionic strengths due to charge screening, we have identified ligands that are well solvated in concentrated brine containing divalent cations and thus provide steric stabilization of silica nanoparticles. Specifically, the hydrodynamic diameter of silica nanoparticles with grafted low molecular weight ligands, a diol ether, [3-(2,3-dihydroxypropoxy)propyl]-trimethoxysilane, and a zwitterionic sulfobetaine, 3-([dimethyl(3-trimethoxysilyl)propyl]ammonio)propane-1-sulfonate, is shown with dynamic light scattering to remain essentially constant, indicating lack of aggregation, at room temperature and up to 80 °C for over 30 days. An extended DLVO model signifies that steric stabilization is strongly dominant against van der Waals attraction for ∼10 nm particles given that these ligands are well solvated even in highly concentrated brine. In contrast, polyethylene glycol oligomers do not provide steric stabilization at elevated temperatures, even at conditions where the ligands are soluble, indicating complicating factors including bridging of the ether oxygens by divalent cations.

Synergistic interactions at the interface of nanoparticles (bare colloidal silica) and surfactant (caprylamidopropyl betaine) led to the generation of viscous and stable CO2‐in‐water (C/W) foams with fine texture at 19.4 MPa and 50°C. Interestingly, neither species generated C/W foams alone. The surfactant became cationic in the presence of CO2 and adsorbed on the hydrophilic silica nanoparticle surfaces resulting in an increase in the carbon dioxide/water/nanoparticle contact angle. The surfactant also adsorbed at the CO2–water interface, reducing interfacial tension to allow formation of finer bubbles. The foams were generated in a beadpack and characterized by apparent viscosity measurements both in the beadpack and in a capillary tube viscometer. In addition, the macroscopic foam stability was observed visually. The foam texture and viscosity were tunable by controlling the aqueous phase composition. Foam stability is discussed in terms of lamella drainage, disjoining pressure, interfacial viscosity, and hole formation. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3490–3501, 2013