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.

Summary The low viscosity and density of carbon dioxide (CO2) usually result in the poor sweep efficiency in CO2-flooding processes, especially in heterogeneous formations. Foam is a promising method to control the mobility and thus reduce the CO2 bypass because of the gravity override and heterogeneity of formations. A switchable surfactant, Ethomeen C12, has been reported as an effective CO2-foaming agent in a sandpack with low adsorption on pure-carbonate minerals. Here, the low mobility of Ethomeen C12/CO2 foam at high temperature (120 °C), high pressure (3,400 psi), and high salinity [22 wt% of total dissolved solids (TDS)] was demonstrated in Silurian dolomite cores and in a wide range of foam qualities. The influence of various parameters, including aqueous solubility, thermal and chemical stability, flow rate, foam quality, salinity, temperature, and minimum-pressure gradient (MPG), on CO2 foam was discussed. A local-equilibrium foam model, the dry-out foam model, was used to fit the experimental data for reservoir simulation.

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.

The utilization of nonionic surfactants for stabilization of CO2 foams has been limited by low aqueous solubilities at elevated temperatures and salinities. In this work, a nonionic surfactant C12–14(EO)22 with a high degree of ethoxylation resulted in a high cloud point temperature of 83 °C even in 90 g/L NaCl brine. Despite the relatively high hydrophilic–CO2-philic balance, the surfactant adsorption at the C–W interface lowered the interfacial tension to ∼7 mN/m at a CO2 density of ∼0.85 g/mL, as determined with captive bubble tensiometry. The adsorption was sufficient to stabilize a CO2-in-water (C/W) foam with an apparent viscosity of ∼7 cP at 80 °C, essentially up to the cloud point temperature, in the presence of 90 g/L NaCl brine in a 30 darcy sand pack. In a 1.2 darcy glass bead pack, the apparent viscosity of the foam in the presence of 0.8% total dissolved solids (TDS) brine reached the highest viscosity of ∼350 cP at 60% foam quality (volume percent CO2) at a low superficial velocity of 6 ft/day. Shear-thinning behavior was observed in both the glass bead pack and the sand pack irrespective of the permeability difference. In addition, C12–14(EO)22 stabilized C/W foam with an apparent viscosity of 80–100 cP in a 49 mdarcy dolomite core formed through a coinjection and a surfactant-alternating-gas process. The dodecane–0.8% TDS brine partition coefficient for C12–14(EO)22 was below 0.1 at 40 °C and 1 atm. The formation of strong foam in the porous media and the low oil–brine partition coefficient indicate C12–14(EO)22 has potential for CO2-enhanced oil recovery.

Despite significant interest in CO 2 foams for EOR, very few studies have reported stable foams at high temperatures and high salinities, which are often encountered in the Middle East and elsewhere. Stable CO 2 /water (C/W) foams at high temperatures up to 120 o C and salinities have been achieved with ethoxylated cationic surfactants. The surfactants were shown to stabilize C/W foams with high salinity brine with NaCl concentration up to 182 g/L at 120 °C, 3400 psia, and to form unstable dodecane/water emulsions with the 120 g/L NaCl brine solutions. Thus, the foams have the potential to provide mobility control to prevent loses of CO 2 in high permeability regions, but simultaneously allow high permeability in the presence of residual oil. The surfactants are soluble in CO 2 and thus may be injected in the CO 2 phase to simplify the EOR process. The aqueous solubility of the surfactant at high temperatures is enhanced with the appropriate number of EO groups on the amine head group. Viscosities of high-pressure C/W foams (emulsions) formed with these surfactants were investigated by capillary rheology. These hybrid cationic/nonionic surfactants combine the high cloud points of ionic surfactants with high solubilities in CO 2 of nonionic surfactants. Furthermore, the variation of the tail length and the degree of ethoxylation offer great flexibility for stabilizing CO 2 foams for EOR at high temperatures and high salinities. Ethoxylated cocoamine exhibited lower adsorption on calcite than that on dolomite, given the presence of silica sites in the latter. High divalent ion concentrations in 22% total dissolved solids (TDS) brine contributed to the reduction of surfactant adsorption on silica sites in the dolomite powder.