Thermal Stability of Surfactants for Reservoir Application (includes associated papers 11323 and 11597 )

Abstract

Abstract The thermal stabilities of several sulfonate surfactantsand one nonionic surfactant have been evaluated. Thedecomposition reactions have been observed to followfirst-order kinetics. Consequently, a quantitativemeasure of a surfactant's stability at a given temperatureis its half-life. Furthermore, the activation energy can beestimated from rate data obtained at two or moretemperatures. This permits limited extrapolation of theobserved decomposition rates to lower temperatures forwhich the rates are too low for convenient measurement.The surfactants we investigated are being considered forsteamflood additives and need to be relatively stable atsteam temperatures.None of the surfactants evaluated to date has therequisite stability for use in steamfloods. The most stablepetroleum sulfonate we have investigated has a half-lifeof 11 days at 180 degrees C (356 degrees F). With this half-life, substantial overdosing would be required tomaintain the minimum effective surfactant concentration forthe life of the flood. On the other hand, the estimatedhalflife for this surfactant at 93 degrees C (200 degrees F), calculated by extrapolation, would be 33 years.Tests with the nonionic surfactant, nonylphenoxy-polyethanol, have shown this material to have a very short half-life at steam temperatures, but it doesappear to be more stable at concentrations greater than thecritical micelle concentration(CMC). In limited tests, the sulfonates showed increased stability in the presenceof a 2-M salt solution. Introduction Several chemical additives are being considered for usewith steamfloods to reduce the producing steam/oilratios and to increase oil recovery from steam projects.The emphasis to date has been on inorganic chemicaladditives. Sodium hydroxide has been used in the fieldwithout success. We have been investigating thepotential benefits of using organic surfactants. This hasbeen discusssed recently by Brown et al. and byGopalakrishnan et al. The surfactant would be introducedinto the reservoir along, with the steam at the beginning ofthe steamflood and, possibly, intermittently during the floodprocess. The surfactant would be injected in diluteconcentrations and would be expected to travel in thatportion of the reservoir being flooded by hot water.Although the residual oil saturation in the steam zone has been observed to be very low, residual saturation in thehot water portion of the steamflood is expected to be thenormal waterflood residual. A surfactant in the hot watermay reduce this residual oil saturation. A synergistic effect could be observed between the surfactant and thetemperature to give better performance than would beobserved for a surfactant flood at normal reservoirtemperatures.For the process to work as anticipated, the surfactantmust move in the heated portion of the reservoir, and it must be sufficiently stable at elevated temperatures tofunction as an effective recovery agent for the life of theflood. Therefore, two aspects of the process are beingstudied simultaneously. One of these is the effect oftemperature on adsorption of the surfactants, and theother is the effect of heat on the stability of thesurfactants. The effect of temperature on adsorption will bediscussed in a later paper. The objective of this paper isto discuss the experimental evaluation of the thermalstability of some surfactant types that could haveapplication in reservoir floods. The effect of temperatureon adsorption and stability of these surfactants also willbe important in micellar floods at higher reservoirtemperatures. Experimental Procedures Several anionic and noninoic surfactants were selectedfor evaluation. SPEJ P. 722^