Switchable Nonionic to Cationic Ethoxylated Amine Surfactants for CO2 Enhanced Oil Recovery in High-Temperature, High-Salinity Carbonate Reservoirs
- Yunshen Chen (University of Texas at Austin) | Amro S. Elhag (University of Texas at Austin) | Benjamin M. Poon (University of Texas at Austin) | Leyu Cui (Rice University) | Kun Ma (Rice University) | Sonia Y. Liao (University of Texas at Austin) | Prathima P. Reddy (University of Texas at Austin) | Andrew J. Worthen (University of Texas at Austin) | George J. Hirasaki (Rice University) | Quoc P. Nguyen (University of Texas at Austin) | Sibani L. Biswal (Rice University) | Keith P. Johnston (University of Texas at Austin)
- Document ID
- Society of Petroleum Engineers
- SPE Journal
- Publication Date
- April 2014
- Document Type
- Journal Paper
- 249 - 259
- 2013.Society of Petroleum Engineers
- 5.7.2 Recovery Factors, 5.8.7 Carbonate Reservoir, 2.5.2 Fracturing Materials (Fluids, Proppant)
- foam, CO2, amine, surfactant, EOR
- 5 in the last 30 days
- 805 since 2007
- Show more detail
- View rights & permissions
|SPE Member Price:||USD 10.00|
|SPE Non-Member Price:||USD 30.00|
To improve sweep efficiency for carbon dioxide (CO2) enhanced oil recovery (EOR) up to 120°C in the presence of high-salinity brine (182 g/L NaCl), novel CO2/water (C/W) foams have been formed with surfactants composed of ethoxylated amine headgroups with cocoalkyl tails. These surfactants are switchable from the nonionic (unprotonated amine) state in dry CO2 to cationic (protonated amine) in the presence of an aqueous phase with a pH less than 6. The high hydrophilicity in the protonated cationic state was evident in the high cloudpoint temperature up to 120°C. The high cloudpoint facilitated stabilization of lamellae between bubbles in CO2/water foams. In the nonionic form, the surfactant was soluble in CO2 at 120°C, and 3,300 psia at a concentration of 0.2% (w/w). C/W foams were produced by injecting the surfactant into either the CO2 phase or the brine phase, which indicated good contact between phases for transport of surfactant to the interface. Solubility of the surfactant in CO2 and a favorable C/W partition coefficient are beneficial for transport of surfactant with CO2-flow pathways in the reservoir, to minimize viscous fingering and gravity override. The ethoxylated cocoamine with two ethylene oxide (EO) groups was shown to stabilize C/W foams in a 30-darcy sandpack with NaCl concentrations up to 182 g/L at 120°C, 3,400 psia, and foam qualities from 50 to 95%. The foam produces an apparent viscosity of 6.2 cp in the sandpack and 6.3 cp in a 762-µm-inner-diameter capillary tube (downstream of the sandpack) in contrast with values well below 1 cp without surfactant present. Moreover, the cationic headgroup reduces the adsorption of ethoxylated alkyl amines on calcite, which is also positively charged in the presence of CO2 dissolved in brine. The surfactant partition coefficients (0 to 0.04) favored the water phase over the oil phase, which is beneficial for minimizing losses of surfactant to the oil phase for efficient surfactant usage. Furthermore, the surfactant was used to form C/W foams, without forming stable/viscous oil/water (O/W) emulsions. This selectivity is desirable for mobility control whereby CO2 will have low mobility in regions in which oil is not present and high contact with oil at the displacement front. In summary, the switchable ethoxylated alkyl amine surfactants provide both high cloudpoints in brine and high interfacial activities of ionic surfactants in water for foam generation, as well as significant solubilities in CO2 in the nonionic dry state for surfactant injection.
|File Size||908 KB||Number of Pages||11|
Adams, W.T. and Schievelbein, V.H. 1987. Surfactant Flooding CarbonateReservoirs. SPE Res Eval & Eng 2 (4): 619-626. http://dx.doi.org/10.2118/12686-PA.
Adkins, S.S., Chen, X., Chan, I. et al. 2010a. Morphology and Stability of CO2-in-Water Foams with Nonionic Hydrocarbon Surfactants. Langmuir 26 (8): 5335-5348.
Adkins, S.S., Chen, X., Sanders, A. et al. 2010b. Effect of Branching on theInterfacial Properties of Nonionic Hydrocarbon Surfactants at the Air-Water andCarbon Dioxide-Water Interfaces. J. Colloid and Interface Sci. 346 (2): 455-463.
Algharaib, M. 2009. Potential Applications of CO2-EOR in theMiddle East. Paper SPE 120231 presented at the SPE Middle East Oil and Gas Showand Conference, Bahrain, Bahrain, 15-18 March. http://dx.doi.org/10.2118/120231-MS.
Alvarez, J.M., Rivas, H.J., and Rossen, W.R. 2001. Unified Model forSteady-State Foam Behavior at High and Low Foam Qualities. SPE J. 6 (3): 325-333. http://dx.doi.org/10.2118/74141-PA.
Barnes, J.R., Smit, J.P., Smit, J.R. et al. 2008. Development of Surfactantsfor Chemical Flooding at Difficult Reservoir Conditions. Paper SPE 113313 presented at the SPE/DOE Improved Oil Recovery Symposium, Tulsa, Oklahoma,20-23 April. http://dx.doi.org/10.2118/113313-MS.
Borchardt, J.K., Bright, D.B., Dickson, M.K. et al. 1985. Surfactants for CO2 Foam Flooding. Paper SPE 14394 presented at the 60th AnnualTechnical Conference and Exhibition of the Society of Petroleum Engineers, LasVegas, Nevada, 22-26 September. http://dx.doi.org/10.2118/14394-MS.
Chalbaud, C., Robin, M., Lombard, J.M. et al. 2010. Brine/CO2Interfacial Properties and Effects on CO2 Storage in Deep SalineAquifers. Oil & Gas Sci. and Technol. 65 (4):541-555.
Charlton, S.R. and Parkhurst, D.L. 2011. Modules Based on the GeochemicalModel PHREEQC for Use in Scripting and Programming Languages. Computers& Geosci. 37 (10): 1653-1663.
Chen, X., Adkins, S.S., Nguyen, Q.P. et al. 2010. Interfacial Tension andthe Behavior of Microemulsions and Macroemulsions of Water and Carbon DioxideWith a Branched Hydrocarbon Nonionic Surfactant. J. of SupercriticalFluids 55 (2): 712-723.
Eckert, C.A., Knutson, B.L., and Debenedetti, P.G. 1996. SupercriticalFluids as Solvents for Chemical and Materials Processing. Nature 383: 313-318.
Enick, R. and Olsen, D. 2011. Mobility and Conformance Control for CarbonDioxide Enhanced Oil Recovery (CO2-EOR) via Thickeners, Foams andGels—A Detailed Literature Review of 40 Years of Research, DOE/NETL-2012/1540;Activity 4003.200.01.
Enick, R.M. and Olsen, D.K. 2012. Mobility and Conformance Control forCarbon Dioxide Enhanced Oil Recovery (CO2-EOR) Via Thickeners,Foams, and Gels—A Detailed Literature Review of 40 Years of Research, USDepartment of Energy.
Epton, S.R. 1947. A Rapid Method of Analysis for Certain Surface-ActiveAgents. Nature 160: 795-796.
Farajzadeh, R., Andrianov, A., Krastev, R. et al. 2012. Foam-Oil Interactionin Porous Media: Implications for Foam Assisted Enhanced Oil Recovery. Advancesin Colloid and Interface Science, In press.
Florin, E., Kjellander, R., and Eriksson, J.C. 1984. Salt Effects on theClould Point of the Poly(ethylene Oxide)+ Water System. J. Chem. Soc.Faraday Trans. 1: Physical Chemistry in Condensed Phases 80(11): 2889-2910.
Friedmann, F. and Jensen, J.A. 1986. Some Parameters Influencing theFormation and Propagation of Foams in Porous Media. Paper SPE 15087 presentedat the SPE California Regional Meeting of the Society of Petroleum Engineers,Inc., Oakland, California, 2-4 April. http://dx.doi.org/10.2118/15087-MS.
Gozalpour, F., Ren, S.R., and Tohidi, B. 2005. CO2 EOR and Storgein Oil Reservoirs. Oil & Gas Sci. and Technol. 60 (3):537-546.
Gupta, R.B. and Shim, J. 2007. Solubility in Supercritical CarbonDioxide. Boca Raton, Florida: CRC Press.
Heller, J.P. 1994. CO2 Foams in Enhanced Oil Recovery. Foams:Fundamentals and Applications in the Petroleum Industry 242: 201-234.
Hirasaki, G.J., Miller, C.A., and Puerto, M. 2011. Recent Advances inSurfactant EOR. SPE J. 16 (4): 889-907. http://dx.doi.org./10.2118/115386-PA.
Holm, L.W. and Josendal, V.A. 1974. Mechanisms of Oil Displacement by CarbonDioxide. J. Pet Tech 26 (12): 1427-1438. http://dx.doi.org/10.2118/4736-PA.
Holmes, J.D., Ziegler, K.J., Audriani, M. et al. 1999. Buffering the AqueousPhase PH in Water-in-CO2 Microemulsions. J. Phys. Chem. B 103: 5703-5711.
Hulbers, P.D.T., Shah, D.O., and Katritzky, A.R. 1997. Predicting SurfactantCloud Point from Molecular Structure. J. Colloid and Interface Sci. 198 (1): 132-136.
Johnston, K.P. and Da Rocha, S.R.P. 2009. Colloids in Supercritical FluidsOver the Last 20 Years and Future Directions. J. Supercritical Fluids 47: 523-530.
Kahlweit, M. 1995. How To Prepare Microemulsions at Prescribed Temperature,Oil and Brine. J. Phys. Chem. 99: 1281-1284.
Kosmulski, M. 2001. Chemical Properties of Material Surfaces. Vol.viii, 753 pp, New York: Marcel Dekker.
Kuhlman, M.I. 1990. Visualizing the Effect of Light Oil on CO2Foams. J. Pet Tech 42 (7): 902-908. http://dx.doi.org/10.2118/17356-PA.
Lee, H.O., Heller, J.P., and Hoefer, A.M.W. 1991. Change in ApparentViscosity of Carbon Dioxide Foam with Rock Permeability. SPE Res Eval &Eng: 421-428.
Lemert, R.M., Fuller, R.A., and Johnston, K.P. 1990. Reverse Micelles inSupercritical Fluids. 3. Amino Acid Solubilization in Ethane and Propane. J.Phys. Chem. 94: 6021.
Levitt, D.B., Jackson, A., Heinson, C. et al. 2009. Identification andEvaluation of High-Performance EOR Surfactants. SPE Res Eval & Eng 12 (2): 243-253. http://dx.doi.org/10.2118/100089-PA.
Li, J., Bai, D., and Chen, B. 2009. Effects of Additives on the Cloud Pointsof Selected Nonionic Linear Ethoxylated Alcohol Surfactants. Colloids andSurfaces A: Physicochemical and Engineering Aspects 346 (1-3):237-243.
Liu, S., Zhang, D.L., Yan, W. et al. 2008. Favorable Attributes ofAlkaline-Surfactant-Polymer Flooding. SPE J. 13 (1): 5-16.http://dx.doi.org/10.2118/99744-PA.
Liu, Y., Jessop, P.G., Cunningham, M. et al. 2006. Switchable Surfactants.Science 313 (5789): 958-960.
McFann, G.J. 1993. Formation and Phase Behavior of Reverse Micelles andMicroemulsions in Supercritical Fluid Ethane, Propane and Carbon Dioxide,University of Texas, Austin, Texas, 420 pp.
McFann, G.J. and Johnston, K.P. 1993. Phase Behavior of Nonionic Surfactantsin Light Alkanes. Langmuir 9: 2942.
McLendon, W.J., Koronais, P., McNulty, S. et al. 2012. Assessment ofCO2-Soluble Surfactants for Mobility Reduction Using MobilityMeasurements and CT Imaging. Paper SPE 154205 presented at the SPE Improved OilRecovery Symposium, Tulsa, Oklahoma, 14-18 April. http://dx.doi.org/10.2118/154205-MS.
O'Neill, M.L., Cao, Q., Fang, R. et al. 1998. Solubility of Homopolymers andCopolymers in Carbon Dioxide. Ind. Eng. Chem. Res. 37: 3067-3079.
Prokop, R.M., Jyoti, A., Eslamian, M. et al. 1998. A Study of CaptiveBubbles With Axisymmetric Drop Shape Analysis. Colloids and Surfaces, A:Physicochemical and Engineering Aspects 131 (1-3): 231-247. http://dx.doi.org/10.1016/S0927-7757(96)03940-4.
Puerto, M., Hirasaki, G.J., and Miller, C.A. 2010. Surfactant Systems forEOR in High-Temperature, High-Salinity Environments. Paper SPE 129675 presentedat the 2010 SPE Improved Oil Recovery Symposium, Tulsa, Oklahoma. http://dx.doi.org.10.2118/129675-MS.
Puerto, M., Hirasaki, G.J., Miller, C.A. et al. 2012. Surfactant Systems forEOR in High-Temperature, High-Salinity Environments. SPE J. 17 (1): 11-19. http://dx.doi.org/10.2118/129675-PA.
Qun, X., Vasudevan, T.V., and Somasundaran, P. 1991. Adsorption of AnionicNonionic and Cationic Nonionic Surfactant Mixtures on Kaolinite. J. Colloidand Interface Sci. 142 (2): 528-534.
Reck, R.A. 1990. Cationic Surfactants Derived From Nitriles. In CationicSurfactant Organic Chemistry, 163-186, ed. J.M. Richmond, New York: MarcelDekker, Inc.
Ren, G., Zhang, H., and Nguyen, Q.P. 2011. Effect of Surfactant PartitioningBetween CO2 and Water on CO2 Mobility Control inHydrocarbon Reservoirs. Paper SPE 145102 presented at the SPE Enhanced OilRecovery Conference, Kuala Lumpur, Malaysia, 19-21 July. http://dx.doi.org/10.2118/145102-MS.
Renkema, W.J. and Rossen, W.R. 2007. Success of SAG Foam Processes inHeterogeneous Reservoirs. Paper SPE 110408 presented at the SPE AnnualTechnical Conference and Exhibition, Anaheim, California, 11-14 November. http://dx.doi.org/10.2118/110408-MS.
Richmond, J.M. 1990. Cationic Surfactants. Surfactant Science series,34, New York.
Rosen, M.J. 2004. Surfactants and Interfacial Phenomena. New York:John Wiley & Sons, Inc.
Rossen, W.R. 1996a. Foams in Enhanced Oil Recovery. In Foams: Theory,Measurements, and Applications, ed. R.K. Prudhomme and S.A. Khan, New York:Marcel Dekker.
Rossen, W.R. 1996b. Theory, Measurements, and Applications. Foams.New York: Marcel Dekker.
Rossen, W.R. and Wang, U. 1999. Modeling Foams for Acid Diversion. SPEJ. 4 (2): 92-100. http://dx.doi.org/10.2118/56396-PA.
Siracusa, P.A. and Somasundaran, P. 1986. Adsorption Desorption andHysteresis of Sulfonates on Kaolinite—pH Effects. J. Colloid and InterfaceSci. 114 (1): 184-193.
Smith, P.G., Dhanuka, V.V., Hwang, H.S. et al. 2007. Tertiary Amine Estersfor Carbon Dioxide Based Emulsions. Ind. Eng. Chem. Res. 46(8): 2473-2480.
Stalkup, F.I. 1978. Carbon Dioxide Miscible Flooding: Past, Present, andOutlook for the Future. J. Pet Tech 30 (8): 1102-1112. http://dx.doi.org/10.2118/7042-PA.
Stevens, S., Kunskraa, V., and O'Donnell, J. 1999. Enhanced Oil RecoveryScoping Study. Palo Alto, California: EPRI.
Szulczewski, M.L., Cueto-Felgueroso, L., and Juanes, R. 2009. Scaling ofCapillary Trapping in Unstable Two-Phase Flow: Application to CO2Sequestration in Deep Saline Aquifers. Energy Procedia 1:3421-3428.
Tabatabal, A., Gonzalez, M.V., Harwell, J.H. et al. 1993. ReducingSurfactant Adsorption in Carbonated Reservoirs. SPE Res Eng 8 (2): 117-122. http://dx.doi.org/10.2118/24105-PA.
Tsau, J., Yaghoobi, H., and Grigg, R.B. 1998. Smart Foam To Improve OilRecovery in Heterogeneous Porous Media. Paper SPE 39677 presented at theSPE/DOE Improved Oil Recovery Symposium, Tulsa, Oklahoma, 19-22 April. http://dx.doi.org/10.2118/39677-MS.
Wolthers, M., Charlet, L., and Van Cappellen, P. 2008. The Surface Chemistryof Divalent Metal Carbonate Minerals; A Critical Assessment of Surface Chargeand Potential Data Using the Charge Distribution Multi-Site Ion ComplexationModel. Am. J. of Sci. 308 (8): 905-941.
Zhu, T., Ogbe, D.O., and Khataniar, S. 2004. Improving the Foam Performancefor Mobility Control and Improved Sweep Efficiency in Gas Flooding.Industrial & Eng. Chem. Res. 43: 4413-4421.