Using Biosurfactants Produced from Agriculture Process Waste Streams to Improve Oil Recovery in Fractured Carbonate Reservoirs

This report describes the progress of our research during the first 30 months (10/01/2004 to 03/31/2007) of the original three-year project cycle. The project was terminated early due to DOE budget cuts. This was a joint project between the Tertiary Oil Recovery Project (TORP) at the University of Kansas and the Idaho National Laboratory (INL). The objective was to evaluate the use of low-cost biosurfactants produced from agriculture process waste streams to improve oil recovery in fractured carbonate reservoirs through wettability mediation. Biosurfactant for this project was produced using Bacillus subtilis 21332 and purified potato starch as the growth medium. The INL team produced the biosurfactant and characterized it as surfactin. INL supplied surfactin as required for the tests at KU as well as providing other microbiological services. Interfacial tension (IFT) between Soltrol 130 and both potential benchmark chemical surfactants and crude surfactin was measured over a range of concentrations. The performance of the crude surfactin preparation in reducing IFT was greater than any of the synthetic compounds throughout the concentration range studied but at low concentrations, sodium laureth sulfate (SLS) was closest to the surfactin, and was used as the benchmark in subsequent studies. Core characterization was carried out using both traditional flooding techniques to find porosity and permeability; and NMR/MRI to image cores and identify pore architecture and degree of heterogeneity. A cleaning regime was identified and developed to remove organic materials from cores and crushed carbonate rock. This allowed cores to be fully characterized and returned to a reproducible wettability state when coupled with a crude-oil aging regime. Rapid wettability assessments for crushed matrix material were developed, and used to inform slower Amott wettability tests. Initial static absorption experiments exposed limitations in the use of HPLC and TOC to determine surfactant concentrations. To reliably quantify both benchmark surfactants and surfactin, a surfactant ion-selective electrode was used as an indicator in the potentiometric titration of the anionic surfactants with Hyamine 1622. The wettability change mediated by dilute solutions of a commercial preparation of SLS (STEOL CS-330) and surfactin was assessed using two-phase separation, and water flotation techniques; and surfactant loss due to retention and adsorption on the rock was determined. Qualitative tests indicated that on a molar basis, surfactin is more effective than STEOL CS-330 in altering wettability of crushed Lansing-Kansas City carbonates from oil-wet to water-wet state. Adsorption isotherms of STEOL CS-330 and surfactin on crushed Lansing-Kansas City outcrop and reservoir material showed that surfactin has higher specific adsorption on these oomoldic carbonates. Amott wettability studies confirmed that cleaned cores are mixed-wet, and that the aging procedure renders them oil-wet. Tests of aged cores with no initial water saturation resulted in very little spontaneous oil production, suggesting that water-wet pathways into the matrix are required for wettability change to occur. Further investigation of spontaneous imbibition and forced imbibition of water and surfactant solutions into LKC cores under a variety of conditions--cleaned vs. crude oil-aged; oil saturated vs. initial water saturation; flooded with surfactant vs. not flooded--indicated that in water-wet or intermediate wet cores, sodium laureth sulfate is more effective at enhancing spontaneous imbibition through wettability change. However, in more oil-wet systems, surfactin at the same concentration performs significantly better.

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