Curvature-Based Equation of State for Microemulsion-Phase Behavior
- Victor A. Torrealba (King Abdullah University of Science and Technology) | Russell T. Johns (Pennsylvania State University) | Hussein Hoteit (King Abdullah University of Science and Technology)
- Document ID
- Society of Petroleum Engineers
- SPE Journal
- Publication Date
- April 2019
- Document Type
- Journal Paper
- 647 - 659
- 2019.Society of Petroleum Engineers
- Micellar Curvature, Microemulsion Phase Behavior, Surfactant Flooding, Phase Transitions, Surfactant-Polymer Flooding
- 2 in the last 30 days
- 226 since 2007
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An accurate description of the microemulsion-phase behavior is critical for many industrial applications, including surfactant flooding in enhanced oil recovery (EOR). Recent phase-behavior models have assumed constant-shaped micelles, typically spherical, using netaverage curvature (NAC), which is not consistent with scattering and microscopy experiments that suggest changes in shapes of the continuous and discontinuous domains. On the basis of the strong evidence of varying micellar shape, principal micellar curves were used recently to model interfacial tensions (IFTs). Huh’s scaling equation (Huh 1979) also was coupled to this IFT model to generate phase-behavior estimates, but without accounting for the micellar shape.
In this paper, we present a novel microemulsion-phase-behavior equation of state (EoS) that accounts for changing micellar curvatures under the assumption of a general-prolate spheroidal geometry, instead of through Huh’s equation. This new EoS improves phase-behavior-modeling capabilities and eliminates the use of NAC in favor of a more-physical definition of characteristic length. Our new EoS can be used to fit and predict microemulsion-phase behavior irrespective of IFT-data availability. For the cases considered, the new EoS agrees well with experimental data for scans in both salinity and composition. The model also predicts phase-behavior data for a wide range of temperature and pressure, and it is validated against dynamic scattering experiments to show the physical significance of the approach.
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Acosta, E. J., Szekeres, E., Sabatini, D. A. et al. 2002. Net-Average Curvature Model for Solubilization and Supersolubilization in Surfactant Microemulsions. Langmuir 19 (1): 186–195. https://doi.org/10.1021/la026168a.
Acosta, E. J. 2008. The HLD-NAC Equation of State for Microemulsions Formulated With Nonionic Alcohol Ethoxylate and Alkylphenol Ethoxylate Surfactants. Colloids and Surfaces A Physicochemical and Engineering Aspects 320 (1–3): 193–204. https://doi.org/10.1016/j,colsurfa.2008.01.049.
Acosta, E. J., Kiran, S. K., and Hammond, C. E. 2012. The HLD-NAC Model for Extended Surfactant Microemulsions. Journal of Surfactants and Detergents 15 (4): 495–504. https://doi.org/10.1007/s11743-012-1343-2.
Austad, T. and Strand, S. 1996. Chemical Flooding of Oil Reservoirs 4. Effects of Temperature and Pressure on the Middle-Phase Solubilization Parameters Close to Optimum Flood Conditions. Colloids and Surfaces A: Physicochemical and Engineering Aspects 108 (2–3): 243–252. https://doi.org/10.1016/0927-7757(95)03406-4.
Berghaus, M., Paulus, M., Salmen, P. et al. 2016. Near-Surface and Bulk Behavior of Bicontinuous Microemulsions Under High-Pressure Conditions. The Journal of Physical Chemistry B 120 (29): 7148–7153. https://doi.org/10.1021/acs.jpcb.6b05639.
Chandra, P. and Safran, S. A. 1991. Structure Factor for Microemulsions With Finite Spontaneous Curvature. Langmuir 7 (9): 1849–1854. https://doi.org/10.1021/la00057a005.
Davis, H. T. 1994. Factors Determining Emulsion Type: Hydrophile-Lipophile Balance and Beyond. Colloids and Surfaces A: Physicochemical and Engineering Aspects 91: 9–24. https://doi.org/10.1016/0927-7757(94)02929-6.
Debye, P., Anderson Jr., H. R., and Brumberger, H. 1957. Scattering by an Inhomogeneous Solid. II. The Correlation Function and Its Application. Journal of Applied Physics 28 (6): 679–683. https://doi.org/10.1063/1.1722830.
De Gennes, P. G. and Taupin, C. 1982. Microemulsions and the Flexibility of Oil/Water Interfaces. The Journal of Physical Chemistry 86 (13): 2294–2304. https://doi.org/10.1021/j100210a011.
Ghosh, S. and Johns, R. T. 2016a. An Equation-of-State Model to Predict Surfactant/Oil/Brine-Phase Behavior. SPE J. 21 (4): 106–125. SPE-170927-PA. https://doi.org/10.2118/170927-PA.
Ghosh, S. and Johns, R. T. 2016b. Dimensionless Equation of State to Predict Microemulsion Phase Behavior. Langmuir 32 (35): 8969–8979. https://doi.org/10.1021/acs.langmuir.Gb02666.
Healy, R. N. and Reed, R. L. 1974. Physicochemical Aspects of Microemulsion Flooding. SPE J. 14 (5): 491–501. SPE-4583-PA. https://doi.org/10.2118/4583-PA.
Hu, Y. and Matthys, E. F. 1995. Characterization of Micellar Structure Dynamics for a Drag-Reducing Surfactant Solution Under Shear: Normal Stress Studies and Flow Geometry Effects. Rheologica Acta 34 (5): 450–460. https://doi.org/10.1007/BF00396558.
Huh, C. 1983. Equilibrium of a Microemulsion That Coexists With Oil or Brine. SPE J. 23 (5): 829–847. SPE-10728-PA. https://doi.org/10.2118/10728-PA.
Huh, C. 1979. Interfacial Tensions and Solubilizing Ability of a Microemulsion Phase That Coexists With Oil and Brine. Journal of Colloid and Interface Science 71 (2): 408–426. https://doi.org/10.1016/0021-9797(79)90249-2.
Jin, L., Budhathoki, M., Jamili, A. et al. 2017. Predicting Microemulsion Phase Behavior Using Physics Based HLD-NAC Equation of State for Surfactant Flooding. Journal of Petroleum Science and Engineering 151: 213–223. https://doi.org/10.1016/j.petrol.2016.12.035.
Kahlweit, M. and Strey, R. 1985. Phase Behavior of Ternary Systems of the Type H2O-Oil-Nonionic Amphiphile (Microemulsions). Angewandte Chemie 24 (8): 654–668. https://doi.org/10.1002/anie.198506541.
Kamei, D. T., King, J. A., Wang, D. I. C. et al. 2002. Understanding Viral Partitioning in Two-Phase Aqueous Nonionic Micellar Systems: 2. Effect of Entrained Micelle-Poor Domains. Biotechnology and Bioengineering 78 (2): 203–216. https://doi.org/10.1002/bit.10194.
Khorsandi, S. and Johns, R. T. 2016. Robust Flash Calculation Algorithm for Microemulsion Phase Behavior. Journal of Surfactants and Detergents 19 (6): 1273–1287. https://doi.org/10.1007/s11743-016-1877-9.
Khorsandi, S. and Johns, R. T. 2017. Robust Flash Calculation Algorithm for Microemulsion Phase Behavior. Patent Cooperation Treaty (PCT: The International Patent System). International Application No. PCT/2017/048727.
Kiran, S. K. and Acosta, E. J. 2010. Predicting the Morphology and Viscosity of Microemulsions Using the HLD-NAC Model. Industrial and Engineering Chemistry Research 49 (7): 3424–3432.
Kiran, S. K. and Acosta, E. J. 2015. HLD-NAC and the Formation and Stability of Emulsions Near the Phase Inversion Point. Industrial & Engineering Chemistry Research 54 (25): 6467–6479. https://doi.org/10.1021/acs.iecr.5b00382.
Lekkerkerker, H. N. W., Kegel, W. K., and Overbeek, J. Th. G. 1996. Phase Behavior of Ionic Microemulsions. Phys. Chem. 100 (3): 206–217. https://doi.org/10.1002/bbpc.19961000305.
Marquez, N., Graciaa, A., Lachaise, J. et al. 2002. Partitioning of Ethoxylated Alkylphenol Surfactants in Microemulsion-Oil-Water Systems: Influence of Physicochemical Formulation Variables. Langmuir 18 (16): 6021–6024. https://doi.org/10.1021/la020199o.
Peltomäki, M., Gompper, G., and Kroll, D. M. 2012. Scattering Intensity of Bicontinuous Microemulsions and Sponge Phases. The Journal of Chemical Physics 136 (13): 134708. https://doi.org/10.1063/1.3701265.
Salager, J. L., Marquez, N., Graciaa, A. et al. 2000. Partitioning of Ethoxylated Octylphenol Surfactants in Microemulsion-Oil-Water Systems: Influence of Temperature and Relation Between Partitioning Coefficient and Physicochemical Formulation. Langmuir 16 (13): 5534–5539. https://doi.org/10.1021/la9905517.
Salter, S. J. 1977. The Influence of Type and Amount of Alcohol on Surfactant-Oil-Brine Phase Behavior and Properties. Presented at the SPE Annual Fall Technical Conference and Exhibition, Denver, 9–12 October. SPE-6843-MS. https://doi.org/10.2118/6843-MS.
Scriven, L. E. 1976. Equilibrium Bicontinuous Structure. Nature 263 (5573): 123–125. https://doi.org/10.1038/263123a0.
Sottmann, T., Strey, R., and Chen, S. H. 1997. A Small-Angle Neutron Scattering Study of Nonionic Surfactant Molecules at the Water-Oil Interface: Area Per Molecule, Microemulsion Domain Size, and Rigidity. Journal of Chemical Physics 106 (15): 6483–6491. https://doi.org/10.1063/1.473638.
Strey, R. 1993. On the Stability Range of Microemulsions: From the Tricritical Point to the Lamellar Phase in Water/Formamide-Octane-CiEj Systems. Berichte der Bunsengesellschaft für physikalische Chemie 97 (5): 742–750. https://doi.org/10.1002/bbpc.19930970517.
Strey, R. 1994. Microemulsion Microstructure and Interfacial Curvature. Colloid & Polymer Science 272 (8): 1005–1019.
Strey, R. 1996. Phase Behavior and Interfacial Curvature in Water-Oil-Surfactant Systems. Current Opinion in Colloid & Interface Science 1 (3): 402–410. https://doi.org/10.1016/S1359-021978.
Talmon, Y. and Prager, S. 1978. Statistical Thermodynamics of Phase Equilibria in Microemulsions. J. Chem. Phys. 69 (7): 2984–2991. https://doi.org/10.1063/1.437016.
Tanford, C. 1972. Micelle Shape and Size. The Journal of Physical Chemistry 76 (21): 3020–3024. https://doi.org/10.1021/j100665a018.
Tanford, C. 1974. Theory of Micelle Formation in Aqueous Solutions. The Journal of Physical Chemistry 78 (24): 2469–2479. https://doi.org/10.1021/j100617a012.
Tartar, H. V. 1955. A Theory of the Structure of the Micelles of Normal Paraffin Chain Salts in Aqueous Solution. J. Phys. Chem. 59 (12): 1195–1199. https://doi.org/10.1021/j150534a004.
Torrealba, V. A. 2017. Thermodynamics of Microemulsion Systems: Partitioning Relationships, Phase Behavior, and Interfacial Tensions. PhD dissertation, Pennsylvania State University, State College, Pennsylvania (December 2017).
Torrealba, V. A. and Johns, R. T. 2017a. Coupled Interfacial Tension and Phase Behavior Model Based on Microscopic Curvatures. Langmuir 33 (47): 13604–13614. https://doi.org/10.1021/acs.langmuir.7b03372.
Torrealba, V A. and Johns, R. T. 2017b. Microemulsion Phase Behavior Equation-of-State Model Using Empirical Trends in Chemical Potentials. SPE J. 23 (3): 819–830. SPE-184555-PA. https://doi.org/10.2118/184555-PA.
Torrealba, V. A. and Johns, R. T. 2018. Partition Coefficient Relations for Improved Equation-of-State Description of Microemulsion Phase Behavior. SPE J. (preprint) SPE-179845-PA. https://doi.org/10.2118/179845-PA.