Application of LC-MS and Methyl Orange Methods for Improved Residual Surfactant Detection in Liquids-Rich Shale Plays

Successful field trials of surfactant-based Production Enhancement (PROE) technology in different shale plays including Permian Basin, Bakken and Eagle Ford indicate that specially tailored surfactant formulations can improve the unconventional well productivity during flowback and production. One major challenge for the operator is to further optimize the surfactant dosage to maximize the economic return. Analysis of the residual surfactant concentration in the produced water (PW) might provide a new path to optimize the surfactant application in the field. Such quantitative measurements can help understand how much surfactant is consumed in the downhole and how much surfactant is in the flowback, and possibly correlate back to the well performance. Additionally, surfactant partitioning and adsorption behaviors can be studied through residual analysis, which will further provide guidance to develop next generation of surfactant formulations. In this study, a liquid chromatography-mass spectrometry (LC-MS) method was developed to accurately measure the residual surfactant concentration in the produced water. The liquid chromatograph (LC) separates the surfactant from sample matrix and avoids the possible interference, and then the mass spectrometer (MS) detects the separated surfactant, signal correlating to the residual concentration. This analytical method provides unrivalled selectivity and specificity compared to other methods reported in the literature. In addition, a Methyl Orange method was developed and can potentially be used in the field for quicker measurements. Produced water samples collected from a Huff-and-Puff treatment in the Permian Basin were evaluated using both methods. Our results indicate that both methods can successfully capture the trend of residual concentration vs. production time. The deviation between LC-MS and Methyl Orange measurements was due to the presence of ADBAC (alkyldimethylbenzylammonium chloride) in the produced water, which is a cationic amine surfactant typically used as biocide in the well stimulation. It produces positive interference and thus leads to a higher residual detection in the Methyl Orange test. Notably, the residual concentration of surfactant in produced water decreased with time after the well was placed back to production, which is consistent with the concept that more surfactant will adsorb to the rock surface or partition into the oil phase over production time. In summary, we believe the LC-MS and Methyl Orange methods can potentially be used to detect residual concentration for any type of surfactant-based applications in unconventional reservoirs including Huff-and-Puff, completion, frac protect, surfactant flooding and re-frac. The field application of surfactant-based chemistry followed by this type of residual analysis can help understand the underlying mechanisms of the surfactant and provide further guidance for production optimization of shales.