Cation Exchange in Porous Media With Broad-Equivalent-Weight Sulfonate Micellar Fluids

Abstract

This paper describes experimental and theoretical studies of cation exchange in porous media with micellar fluids formulated using a broad-equivalent-weight (BEW) sulfonate. The sulfonates can be described as composed of two pseudocomponents a quasi-monosulfonate (the oil-moving pseudo components a quasi-monosulfonate (the oil-moving component) and a quasi-disulfonate (the sulfonate-solubilizing component). With this description and a mass-action model for cation exchange between the micelles, clays, and solution, a match between computer model predictions and results of laboratory single-phase flow tests in Berea sandstone was carried out. The assumptions required are reviewed and independent experimental results presented. With these assumptions and parameter values determined from the Berea history match, satisfactory predictions of divalent cation concentrations in field core experiments have been made. The good predictive capability of this model allows initial screening and development of micellar formulations for specific reservoir applications to be conducted at appropriate hardness levels. Introduction It is well known that the oil recovery performance of a micellar fluid is strongly affected by salinity and hardness (calcium and magnesium divalent cations). This is because they have strong effects on the phase behavior and interfacial tension (IFT) of the surfactant/oil/brine system. It is also well known that the hardness and salinity of the micellar fluid can change significantly as a result of cation exchange and dissolution as the micellar fluid propagates through the reservoir. Since a knowledge of the in-situ levels of salinity and hardness is of primary importance in the screening and development of micellar fluids for field applications, an adequate prediction is necessary. Cation exchange between a brine and the clays within a reservoir rock occurs if the injected fluids have a salinity and hardness different from that of the in-place fluids. Smith, Griffith, and Hill and Lake have studied this problem and have shown the significance of the cation-exchange capacity (CEC) of the clays and the selectivity of the cation species with the clays. The clay selectivity is a measure of the preference of the clay for monovalent vs. divalent cations; for a given brine, smaller values indicate a higher fraction of the clays complexed by the divalent cations. Further, Hill and Lake concluded that the law of mass action is the best model with which to describe the process. Smith, and Hill and Lake, also showed that calcium and magnesium ions have the same selectivity with the clays vs. sodium, and hence they can be treated as a single ionic species. Hill and Lake extended their study to systems containing surfactants. They found that cation exchange in the presence of a surfactant system was complicated by interaction between surfactant and divalent cations. To describe the levels of hardness measured in the presence of surfactant micelles, they postulated the formation of a divalent-cation/surfactant complex and modeled the phenomenon with a mass-action isotherm. Gupta provided phenomenon with a mass-action isotherm. Gupta provided additional data supporting the formation of such a complex. Hirasaki and Lawson proposed a Donnan equilibrium model to describe the association of sodium and calcium with the micelles, and they estimated selectivity values from the resulting expressions. Hirasaki has incorporated a mass-action model, surfactant adsorption, and electroneutrality conditions with the mass balances neglecting dispersion to obtain a description of cation exchange during single-phase-flow in porous media. He has solved the system of equations using a method-of-characteristics approach and has been able to describe the experiments of Hill and Lake and Gupta showing good agreement between experiment and theory. The model is limited to one surfactant species and two cations-one monovalent and one divalent. The surfactant system used by Gupta closely conforms to these limitations. The micellar system used by Hill and Lake, however, was composed of two petroleum sulfonates and sodium alkyl ethoxysulfate (Neodol 25–3S). Nevertheless, Hirasaki assumed the surfactant mixture to be acting as a single surfactant species. This paper deals with the cation exchange that occurs during the propagation of a micellar system containing BEW sulfonate. The objective is to history-match limited tests in Berea cores and then to use the understanding gained and parameter values obtained to predict hardness concentrations in field cores over a wide range of micellar compositions. To correlate the Berea data and to extrapolate to other conditions, the approach of Hirasaki is desirable because of its simplicity. However, the complex composition of the BEW sulfonate micellar system, as well as a desire to include an adsorption isotherm and dispersion-important for small slug processes-precluded the straightforward use of the equations and the solution that he put forward. SPEJ P. 580

Mineral dissolution, precipitation, and ion exchange in surfactant flooding

“…The numerical value of the selectivity factor Ks. Table 1, is in close agreement with data found by other authors (Bruggenwert and Kamphorst, 1982; Chan and Kremesec, 1985;Hirasaki, 1982) for similar types of soils.…”

“…Therefore adsorption is secondary in every experiment provided there is a slight amount of carbonate that dissolves and acts as a buffer which maintains a high pH. Hirasaki (1982) and Chan and Kremesec (1985) have studied surfactant transport with mineral dissolution. To account for the observed surfactant fronts they introduced an empirical adsorption isotherm in their models.…”

Laboratory Evaluation of a Crude-Oil-Sulfonate/Nonionic-Cosurfactant Micellar Fluid

“…S These calculations have been previously performed for CROS/nonionic micellar fluids. 9 For the ionic system considered in this paper, the in-place brine is of low salinity (0.0426 N) but relatively high hardness (0.0193 N). As a result, the clays are about 95% in the hardened state.…”

“…During· the course of ion exchange in the reservoir, sodium will replace ammonium in the micellar fluid. 9 At lower cosurfactant concen- trations, this exchange of sodium for ammonium cations improves brine solubilization and reduces oil solubilization. At higher cosurfactant concentrations, the overall effect is lessened.…”

“…There is a significant difference in the affinity of the clays in Berea for these monovalent cations. 9 Apparently, there is also a difference in the affinity of the sulfonate for these monovalent cations and it can have an effect on the phase behavior.…”