Evaluation and design of surfactant formulations for wettability alteration

Only about 35% of oil is recovered from carbonate reservoirs through primary and secondary flooding because of oil wet surfaces and unfavorable capillary pressures. Surfactants, with their dual hydrophobic and hydrophilic nature have been known to improve oil recovery significantly by lowering oil-water interfacial tension and by altering wettability of surfaces. However, the process of selecting an efficient surfactant for wettability alteration is dependent on several factors, including mineral type, porosity, temperature, salinity, nature of adsorbed oil, molecular structure and surfactant adsorption. Core-flood experiments usually used for evaluating surfactants tend to be time-consuming and provide very little information on the actual mechanism of surfactant action. A fast evaluation scheme is hence required to measure surfactant performances corresponding to the above mentioned parameters. The current work focusses on macro and molecular scale analysis of surfactants to understand relevant structure-property relationships and mechanism of wettability alteration. Surfactants are first evaluated and screened through a series of phase behavior, contact angle and oil-film experiments. The experimental observations have been used to correlate parameters like molecular structure, temperature and brine salinity to macroscopic properties like wettability alteration, adsorption and capillary driving force. Oil-film experiments have been used to understand the surfactant-aided wettability alteration. The role of surfactant adsorption in wettability alteration is investigated by static adsorption experiments. Adsorption isotherms are measured for different surfactant hydrophilicities at different temperatures and surfactant cloud point is used to develop a thermodynamic model explaining the universal surfactant behavior. Along with experiments, molecular dynamics simulations are also performed to understand the mechanism of aggregative adsorption of the nonionic surfactants. To address the issue of high temperature, high salinity applications, mixed surfactant formulations of nonionic surfactants and anionic hydrotropes are developed. Detailed investigations are performed to understand the role of hydrotrope structure, concentration and temperature on the mechanism of aqueous stabilization and adsorption and their effect on wettability alteration. Overall, the current work first establishes a macro and molecular-scale understanding of the phenomenon of surfactant-assisted wettability alteration and associated structure-property relationships. While shorter surfactant hydrophilic units and high temperatures are found to exhibit better wettability alteration, in fact it is proximity to surfactant cloud point which is the determining thermodynamic descriptor. Improved wettability alteration is correlated with surfactant adsorption which occurs in an aggregative manner. It also means there is a tradeoff between surfactant adsorption and wettability alteration. Using this knowledge, surfactant formulations are developed to observe and predict enhanced oil recoveries from representative porous media.Chemical Engineerin