Continuous Flow Synthesis of Petroleum Sulfonates from Crude Oil and Formulation into Nano-Surfactants for Cost Efficient Oil Mobilization

Abstract

The oil mobilization in tertiary mode using chemicals has been shown to be a promising approach. In such technique, surfactants with or without polymers, designed for specific reservoir conditions, are added into water during water flooding to further drive remaining oil out of the porous structure of the reservoir rock into production wells. The success of the method depends on the cost of the chemicals used and the amount of the additional incremental oil mobilization achieved beyond water flooding. Thus, utilizing reservoir-compatible and inexpensive surfactants is a key. Petroleum sulfonates are some of the most abundant and inexpensive surfactants that can be made available at the scale required for efficient oil mobilization operations. However, petroleum sulfonates lack solubility in harsh reservoir conditions which makes them rather inapplicable for reservoirs with high salt content (e.g. > 50,000 ppm) and high temperature (e.g. 100 °C). We have successfully developed a simple, one-step nano-encapsulation technique to transform petroleum sulfonates into nano-sized multi-emulsion droplets in high salinity injection water featuring long-term stability at high temperatures. To further improve the economics and sustainability of such NanoSurfactants (NS), we developed a continuous and cost-effective synthesis process of petroleum sulfonates, directly from crude oil. The in-house-produced sulfonates were then formulated into a NS solution in high salinity injection water utilizing our encapsulation method. Results showed that petroleum sulfonates were successfully synthesized as seen from NMR analysis. The formulated NS was persistently stable at reservoir conditions, altered the wettability of the oil-wet rock as verified by contact angle measurements, and triggered crude oil release from the rock by spontaneous imbibition. This work provides a solution to produce petroleum sulfonates and formulate NS on-site for use in cost-efficient oil mobilization operations in high salinity and high temperature reservoirs.

Wettability-Based Retention of Encapsulated Petroleum Sulfonate in Carbonate Rocks at High-Temperature and High-Salinity Conditions

“…Desirable EOR surfactants should be reachable at a low cost. Petroleum sulfonate (PS) can be economically produced in large quantities locally through direct sulfonation 17 of crude oil or its distillates and is the dominant surfactant used in fields in the 1960s. 4,5 Precipitation of the surfactant at high-temperature and high-salinity (HTHS) conditions had been one of the main reasons impeding its wide application in EOR strategies.…”

“…Sulfonation of crude oil was achieved as reported previously . Ten mL of crude oil was placed into a three-neck round-bottom flask.…”

“…Sulfonation of crude oil was achieved as reported previously. 17 Ten mL of crude oil was placed into a three-neck round-bottom flask. The overhead mixer with a polytetrafluoroethylene (PTFE) coated surface was used to stir the reaction at 400 rpm.…”

“…Desirable EOR surfactants should be reachable at a low cost. Petroleum sulfonate (PS) can be economically produced in large quantities locally through direct sulfonation of crude oil or its distillates and is the dominant surfactant used in fields in the 1960s. , Precipitation of the surfactant at high-temperature and high-salinity (HTHS) conditions had been one of the main reasons impeding its wide application in EOR strategies. Encapsulating PS with the zwitterionic cosurfactant into 10–60 nm oil swollen micelles develops the Nano-Surfactant (NS) with exceptional colloidal and chemical stability in high-salinity brine at 100 °C and shows the efficacy in producing oils through reducing IFT to ultralow values and changing the rock wettability toward more water-wet. − …”