Bulk and Surface Aqueous Speciation of Calcite: Implications for Low-Salinity Waterflooding of Carbonate Reservoirs
- Maxim P. Yutkin (King Abdullah University of Science and Technology) | John Y. Lee (Department of Chemical and Biomolecular Engineering, University of California) | Himanshu Mishra (King Abdullah University of Science and Technology) | Clayton J. Radke (King Abdullah University of Science and Technology) | Tadeusz W. Patzek (King Abdullah University of Science and Technology)
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- Society of Petroleum Engineers
- SPE Kingdom of Saudi Arabia Annual Technical Symposium and Exhibition, 25-28 April, Dammam, Saudi Arabia
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- Document Type
- Conference Paper
- 2016. Society of Petroleum Engineers
- 5.8.7 Carbonate Reservoir, 4.3.3 Aspaltenes, 5.4.1 Waterflooding, 5.4 Improved and Enhanced Recovery, 5.3.6 Chemical Flooding Methods (e.g., Polymer, Solvent, Nitrogen, Immiscible CO2, Surfactant, Vapex), 5 Reservoir Desciption & Dynamics, 5.8 Unconventional and Complex Reservoirs
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Low-salinity waterflooding (LSW) is ineffective when reservoir rock is strongly water wet or when crude oil is not asphaltenic. Success of LSW relies heavily on the ability of injected brine to alter surface chemistry of reservoir rock-brine-crude oil interfaces. LSW in carbonate reservoirs is especially challenging because of high brine salinity and, more importantly, because of high reactivity of the rock minerals. Here, we tackle the complex physicochemical processes in chemically active carbonates flooded with diluted brine that is saturated with atmospheric CO2 and possibly supplemented with additional ionic species, such as sulfates or phosphates. Later work will focus on the important role of crude oil and multicomponent ion-exchange (MIE) in LSW.
When waterflooding carbonate reservoirs, rock equilibrates with the injected brine over short distances. Injected-brine ion speciation is shifted substantially in the presence of reactive-carbonate rock. Our new calculations demonstrate that rock-equilibrated aqueous pH is slightly alkaline quite independent of injected-brine pH. We establish, for the first time, that carbon-dioxide content of a carbonate reservoir, originating from CO2-rich crude oil and gas, plays a dominant role in setting aqueous pH and speciation.
A simple ion-complexing model predicts calcite surface charge as a function of composition of reservoir brine. The surface charge of calcite may be positive or negative depending on speciation of reservoir brine in contact with the calcite. There is no single point of zero charge; all dissolved aqueous species are charge determining. Rock-equilibrated aqueous composition controls calcite surface ion-exchange behavior. At high ionic strength, the electrical double layer collapses and is no longer diffuse. All surface charges are located directly in the inner and outer Helmholtz planes.
Our evaluation of calcite bulk and surface equilibria is preliminary but draws several important inferences about proposed LSW oil-recovery mechanisms. Diffuse double layer expansion (DLE) is not possible unless brine ionic strength is below 0.1 molar. Because of rapid rock/brine equilibration, the dissolution mechanism for releasing adhered oil is eliminated. Also, fines mobilization and concomitant oil release cannot occur because there are few loose fines and clays in a majority of carbonates. LSW cannot be a low interfacial-tension alkaline flood because carbonate dissolution exhausts all injected base near the wellbore and lowers pH to that set by the rock and by formation CO2. In spite of diffuse double-layer collapse in carbonate reservoirs, surface ion-exchange oil release remains feasible, but unproven.
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Alotaibi M. B., Nasr-El-Din H., and Fletcher J. (2011). Electrokinetics of Limestone and Dolomite Rock Particles. SPE Reservoir Evaluation & Engineering, 14(5): pp. 594–603. DOI: 10.2118/148701-PA (cit. on pp. 2,5,7).
Al-Shalabi E. W., Sepehrnoori K., and Pope G. (2014). Geochemical Interpretation of Low Salinity Water Injection in Carbonate Oil Reservoirs. SPE 169101 Presented at SPE Improved Oil Recovery Symposium, 12-16 April, Tulsa, Oklahoma, USA. DOI: 10.2118/169101-MS (cit. on pp. 3, 4).
Arvidson R. S., Ertan I. E., Amonette J. E., and Luttge A. (2003). Variation in Calcite Dissolution Rates:: A Fundamental Problem? Geochimica et Cosmochimica Acta, 67 (9): pp. 1623–1634. DOI: 10.1016/S0016-7037(02)01177-8 (cit. on p. 18).
Bernard G. G. (1967). Effect of Floodwater Salinity on Recovery of Oil from Cores Containing Clays. SPE. DOI: 10.2118/1725-MS (cit. on p. 2).
Brady P. V., Morrow N. R., Fogden A., Deniz V., Loahardjo N., and Winoto A. (2015). Electrostatics and the Low Salinity Effect in Sandstone Reservoirs. Energy and Fuels, 29 (2): pp. 666–677. DOI: 10.1021/ef502474a (cit. on p. 2).
Chandrasekhar S. and Mohanty K. K. (2013). Wettability Alteration with Brine Composition in High Temperature Carbonate Reservoirs. SPE 166280 Presented at SPE Annual Technical Conference and Exhibition, 30 September – 2 October, New Orleans, Louisiana, USA. DOI: 10.2118/166280-MS (cit. on p. 2).
Charlton S. R. and Parkhurst D. L. (2011). Modules Based on the Geochemical Model PHREEQC for Use in Scripting and Programming Languages. Computers & Geosciences, 37(10): pp. 1653–1663. DOI: 10.1016/j.cageo.2011.02.005 (cit. on p. 4).
Chou L., Garrels R. M., and Wollast R. (1989). Comparative Study of the Kinetics and Mechanisms of Dissolution of Carbonate Minerals. Chemical Geology, 78 (3-4): pp. 269–282. DOI: 10.1016/0009-2541(89)90063-6 (cit. on p. 18).
Cubillas P., Köhler S., Prieto M., Chaiïrat C., and Oelkers E. H. (2005). Experimental Determination of the Dissolution Rates of Calcite, Aragonite, and Bivalves. Chemical Geology, 216 (1-2): pp. 59–77. DOI: 10.1016/j.chemgeo.2004.11.009 (cit. on p. 18).
Davis J., James R., and Leckie J. (1978). Surface Ionization and Complexation at the Oxide / Water Interface. Journal of Colloid and Interface Science, 63 (3): pp. 480–499. DOI: 10.1016/S0021-9797(78)80009-5 (cit. on p. 5).
Eisenlohr L., Meteva K., Gabrovšek F., and Dreybrodt W. (1999). The Inhibiting Action of Intrinsic Impurities in Natural Calcium Carbonate Minerals to Their Dissolution Kinetics in Aqueous H2O?CO2 Solutions. Geochimica et Cosmochimica Acta, 63 (7-8): pp. 989–1001. DOI: 10.1016/S0016-7037(98)00301-9 (cit. on p. 18).
Fathi S. J., Austad T., and Strand S. (2010). "Smart Water" as a Wettability Modifier in Chalk: The Effect of Salinity and Ionic Composition. Energy and Fuels, 24 (4): pp. 2514–2519. DOI: 10.1021/ef901304m (cit. on p. 2).
Fenter P., Geissbühler P., Dimasi E., Srajer G., Sorensen L. B., and Sturchio N. C. (2000). Surface Speciation of Calcite Observed in Situ by High-Resolution X-Ray Reflectivity. Geochimica Cosmochimica Acta, 64 (7): pp. 1221–1228. DOI: 10.1016/S0016-7037(99)00403-2 (cit. on p. 4).
Folk R. L. (1959). Practical Petrographic Classification of Limestones. AAPG Bulletin, 43 (1): pp. 1–38. DOI: 10.1306/0BDA5C36-16BD-11D7-8645000102C1865D (cit. on p. 3).
Geissbühler P., Fenter P., DiMasi E., Srajer G., Sorensen L. B., and Sturchio N. C. (2004). Three-Dimensional Structure of the Calcite-Water Interface by Surface X-Ray Scattering. Surface Science, 573 (2): pp. 191–203. DOI: 10.1016/j.susc.2004.09.036 (cit. on p. 4).
Grahame D. C. (1947). The Electrical Double Layer and the Theory of Electrocapillarity. Chemical Reviews, 41 (3): pp. 441501. DOI: 10.1021/cr60130a002 (cit. onp. 5).
Heberling F., Trainor T. P., Lützenkirchen J., Eng P., Denecke M. A., and Bosbach D. (2011). Structure and Reactivity of the Calcite-Water Interface. Journal of Colloid and Interface Science, 354 (2): pp. 843–857. DOI: 10.1016/j.jcis.2010.10.047 (cit. on pp. 4, 5, 7).
Hiemstra T. and Riemsdijk W. H. (1996). A Surface Structural Approach to Ion Adsorption: The Charge Distribution (CD) Model. Journal of Colloid and Interface Science, 179 (2): pp. 488–508. DOI: 10.1006/jcis.1996.0242 (cit. onp. 5).
Hiorth A., Cathles L. M., and Madland M. V. (2010). The Impact of Pore Water Chemistry on Carbonate Surface Charge and Oil Wettability. Transport in Porous Media, 85 (1): pp. 1–21. DOI: 10.1007/s11242-010-9543-6 (cit. on pp.4,5).
Jadhunandan P. P. and Morrow N. R. (1995). Effect of Wettability on Waterflood Recovery for Crude-Oil/Brine/Rock Systems. SPE Reservoir Engineering, 10 (1): pp. 40–46. DOI: 10.2118/22597-pa (cit. onp. 2).
Jones F. O. (1963). Influence of Chemical Composition of Water on Clay Blocking Permeability. Journal of Petroleum Technology, 16 (04): pp. 441–446. DOI: 10.2118/631-PA (cit. onp. 2).
Kerisit S. and Parker S. C. (2004). Free Energy of Adsorption of Water and Calcium on the  Calcite Surface. Chemical Communications, (1): pp. 52–53. DOI: 10.1039/b311928a (cit. on pp. 2,4).
Kim S. and Santamarina J. C. (2015). Geometry-Coupled Reactive Fluid Transport at the Fracture Scale: Application to CO2 Geologic Storage. Geofluids: n/a-n/a. DOI: 10.1111/gfl.12152 (cit. on pp. 3, 18).
Lager A., Webb K. J., Collins R. I., and Richmond D. M. (2008b). LoSal Enhanced Oil Recovery: Evidence of Enhanced Oil Recovery at the Reservoir Scale. SPE 113976 Presented at the 2008 SPE/DOE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, U.S.A., 19-23 April. DOI: 10.2118/113976-MS (cit. on pp. 2, 8).
Lasaga A. C. and Luttge A. (2001). Variation of Crystal Dissolution Rate Based on a Dissolution Stepwave Model. Science, 291 (5512): pp. 2400–2404. DOI: 10.1126/science.1058173 (cit. on p. 18).
Lashkarbolooki M., Riazi M., Hajibagheri F., and Ayatollahi S. (2016). Low Salinity Injection into Asphaltenic-Carbonate Oil Reservoir, Mechanistical Study. Journal of Molecular Liquids, 216: pp. 377–386. DOI: 10.1016/j.molliq.2016.01.051 (cit. on pp. 2, 4).
Levine S., Mingins J., and Bell G. M. (1967). The Discrete-Ion Effect in Ionic Double-Layer Theory. Journal of Electro- analytical Chemistry and Interfacial Electrochemistry, 13 (3): pp. 280–329. DOI: 10.1016/0022-0728(67)80125-6 (cit. on p. 5).
Lu P., Wang Q., Chen T., and Chang F. (2016). A New Approach for Modeling Scale Formation during Water Injection into Carbonate Reservoirs. SPE-KSA-141-MS Presentated at the SPE Kingdom of Saudi Arabia Annual Technical Symposium and Exhibition held in Dammam, Saudi Arabia, 25-28 April 2016. (Cit. on p. 3).
Möller P. and Sastri C. S. (1974). Estimation of the Number of Surface Layers of Calcite Involved in Ca - 45Ca Isotopic Exchange with Solution. Zeitschrift für Physikalische Chemie, 89 (1-4): pp. 80–87. DOI: 10.1524/zpch.1974.89.1-4.080 (cit. on p. 5).
Morrow N. R. and Buckley J. (2013). Improved Oil Recovery by Low-Salinity Waterflooding. Journal of Petroleum Technology, 63 (05): pp. 106–112. DOI: 10.2118/129421-JPT (cit. onp. 2).
Morse J. W. and Arvidson R. S. (2002). The Dissolution Kinetics of Major Sedimentary Carbonate Minerals. Earth-Science Reviews, (1-2): pp. 51–84. DOI: 10.1016/S0012-8252(01)00083-6 (cit. on pp. 17, 18).
Mugele F., Siretanu I., Kumar N., Bera B., Wang L., Ruiter R. de, Maestro A., Duits M., Ende D., and Collins I. (2016). Insights from Ion Adsorption and Contact-Angle Alteration at Mineral Surfaces for Low-Salinity Waterflooding. SPE Journal. DOI: 10.2118/169143-PA (cit. on p. 2).
Myint P. C. and Firoozabadi A. (2015). Thin Liquid Films in Improved Oil Recovery from Low-Salinity Brine. Current Opinion in Colloid and Interface Science, 20 (2): pp. 105–114. DOI: 10.1016/j.cocis.2015.03.002 (cit. on pp. 2, 7).
Nystrom R. (2001). The Influence of Na+, Ca2+, Ba2+, and La3+ on the Zeta Potential and the Yield Stress of Calcite Dispersions. Journal of Colloid and Interface Science, 242 (1): pp. 259–263. DOI: 10.1006/jcis.2001.7766 (cit. on p. 5).
Palandri J. L. and Kharaka Y. K. (2004). A Compilation of Rate Parameters of Water-Mineral Interaction Kinetics for Application to Geochemical Modeling. U.S. Geological Survey Open File Report (OF 2004-1068). National Energy Technology Laboratory - United States Department of Energy, Menlo Park, California March 2004 (cit. on p. 18).
Peng J., Tang G.-Q., and Kovscek A. (2009). Oil Chemistry and Its Impact on Heavy Oil Solution Gas Drive. Journal of Petroleum Science and Engineering, 66 (1–2): pp. 47–59. DOI: 10.1016/j.petrol.2009.01.005 (cit. on p. 18).
Pierre A., Lamarche J. M., Mercier R., Foissy A., and Persello J. (1990). Calcium as Potential Determining Ion in Aqueous Calcite Suspensions. Journal of Dispersion Science and Technology, 11 (6): pp. 611–635. DOI: 10.1080/01932699008943286 (cit. onp. 5).
Plummer L. N., Wigley T. M. L., and Parkhurst D. L. (1978). The Kinetics of Calcite Dissolution in CO2-Water Systems at 5 to 60 °C and 0.0 to 1.0 atm CO2. American Journal of Science, 278 (2): pp. 179–216. DOI: 10.2475/ajs.278.2.179 (cit. on p. 18).
Pokrovsky O. S., Mielczarski J. a., Barres O., and Schott J. (2000). Surface Speciation Models of Calcite and Dolomite/Aqueous Solution Interfaces and Their Spectroscopic Evaluation. Langmuir, 16 (6): pp. 2677–2688. DOI: 10.1021/la980905e (cit. on pp. 4, 5).
Puntervold T., Strand S., Ellouz R., and Austad T. (2015). Modified Seawater As a Smart EOR Fluid in Chalk. Journal of Petroleum Science and Engineering, 133: pp. 440–443. DOI: 10.1016/j.petrol.2015.06.034 (cit. on pp. 2, 5, 8).
Rezaeidoust A., Puntervold T., Strand S., and Austad T. (2009). Smart Water As Wettability Modifier in Carbonate and Sandstone: A Discussion of Similarities/Differences in the Chemical Mechanisms. Energy and Fuels, 23 (9): pp. 44794485. DOI: 10.1021/ef900185q (cit. on p. 2).
Ricci M., Spijker P., Stellacci F., Molinari J.-F., and Voitchovsky K. (2013). Direct Visualization of Single Ions in the Stern Layer of Calcite. Langmuir, 29 (7): pp. 2207–2216. DOI: 10.1021/la3044736 (cit. on pp. 2, 4).
Robin M., Combes R., and Rosenberg E. (1999). Cryo-SEM and ESEM: New Techniques to Investigate Phase Interactions Within Reservoir Rocks. SPE 56829 Presented at SPE Annual Technical Conference and Exhibition, 2: pp. 519–525. DOI: 10.2523/56829-MS (cit. on p. 2).
Robin M., Rosenberg E., and Fassi-Fihri O. (1995). Wettability Studies at the Pore Level: A New Approach by Use of Cryo-SEM. SPE Formation Evaluation, 10(1): pp. 11–19. DOI: 10.2118/22596-PA (cit. onp.2).
Sakuma H., Andersson M. P., Bechgaard K., and Stipp S. L. S. (2014). Surface Tension Alteration on Calcite, Induced by Ion Substitution. Journal of Physical Chemistry C, 118 (6): pp. 3078–3087. DOI: 10.1021/jp411151u (cit. on pp. 2,4).
Salem M. R., Mangood A. H., and Hamdona S. K. (1994). Dissolution of Calcite Crystals in the Presence of Some Metal Ions. Journal of Materials Science, 29 (24): pp. 6463–6467. DOI: 10.1007/BF00354005 (cit. on p. 18).
Sheng J. J. (2014). Critical Review of Low-Salinity Waterflooding. Journal of Petroleum Science and Engineering, 120: pp. 216–224. DOI: 10.1016/j.petrol.2014.05.026 (cit. on pp. 2, 7).
Siffert D. and Fimbel P. (1984). Parameters Affecting the Sign and Magnitude of the Eletrokinetic Potential of Calcite. Colloids and Surfaces, 11 (3-4): pp. 377–389. DOI: 10.1016/0166-6622(84)80291-7 (cit. onp. 5).
Sjöblom J., Simon S., and Xu Z. (2015). Model Molecules Mimicking Asphaltenes. Advances in Colloid and Interface Science, 218: pp. 1–16. DOI: 10.1016/j.cis.2015.01.002 (cit. on p. 18).
Sorbie K. S. and Collins I. R. (2010). A Proposed Pore-Scale Mechanism for How Low Salinity Waterflooding Works. SPE 129833 Presented at the SPE Improved Oil Recovery Symposium, 24-28 April, Tulsa, Oklahoma, USA. DOI: 10.2118/129833-MS (cit. on pp. 2, 8).
Strand S., Høgnesen E. J., and Austad T. (2006). Wettability Alteration of Carbonates - Effects of Potential Determining Ions (Ca2+ and SO42-) and Temperature. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 275 (1-3): pp. 1–10. DOI: 10.1016/j.colsurfa.2005.10.061 (cit. on pp. 2, 8).
Tang G.-Q. and Morrow N. R. (1997). Salinity, Temperature, Oil Composition, and Oil Recovery by Waterflooding. SPE Reservoir Engineering, 12: pp. 269–276. DOI: 10.2118/36680-PA (cit. onp. 2).
Tang G.-Q. and Morrow N. R. (2002). Injection of Dilute Brine and Crude Oil/Brine/Rock Interactions. Washington DC American Geophysical Union Geophysical Monograph Series, 129: pp. 171–179. DOI: 10.1029/129GM16 (cit. onp. 2).
Tang G.-Q. and Morrow N. R. (1999). Influence of Brine Composition and Fines Migration on Crude Oil/Brine/Rock Interactions and Oil Recovery. Journal of Petroleum Science and Engineering, 24 (2-4): pp. 99–111. DOI: 10.1016/S0920-4105(99)00034-0 (cit. onp. 2).
Thompson D. W. and Pownall P. G. (1989). Surface Electrical Properties of Calcite. Journal of Colloid and Interface Science, 131 (1): pp. 74–82. DOI: 10.1016/0021-9797(89)90147-1 (cit. on pp. 5, 7).
Vaidya R. N. and Fogler H. S. (1990). Formation Damage Due to Colloidally Induced Fines Migration. Colloids and Surfaces, 50: pp. 215–229. DOI: 10.1016/0166-6622(90)80265-6 (cit. onp. 2).
Van Cappellen P., Charlet L., Stumm W., and Wersin P. (1993). A Surface Complexation Model of the Carbonate Mineral- Aqueous Solution Interface. Geochimica Cosmochimica Acta, 57 (15): pp. 3505–3518. DOI: 10.1016/0016-7037(93)90135-J (cit. on pp. 5, 7).
Wolthers M., Charlet L., and Van Cappellen P. (2008). The Surface Chemistry of Divalent Metal Carbonate Minerals: A Critical Assessment of Surface Charge and Potential Data Using the Charge Distribution Multi-Site Ion Complexation Model. American Journal of Science, 308 (8): pp. 905–941. DOI: 10.2475/08.2008.02 (cit. on pp.5,7).
Yildiz H. O. and Morrow N. R. (1996). Effect of Brine Composition on Recovery of Moutray Crude Oil by Waterflooding. Journal of Petroleum Science and Engineering, 14 (3-4): pp. 159–168. DOI: 10.1016/0920-4105(95)00041-0 (cit. on p. 2).
Yousef A. A., Al-Saleh S., Al-Kaabi A., and Al-Jawfi M. (2011). Laboratory Investigation of the Impact of Injection-Water Salinity and Ionic Content on Oil Recovery from Carbonate Reservoirs. SPE Keservoir Evaluation & Engineering, 14 (5): pp. 578–593. DOI: 10.2118/137634-PA (cit. onp. 2).
Zahid A., Shapiro A. A., and Skauge A. (2012). Experimental Studies of Low Salinity Water Flooding in Carbonate Reservoirs: A New Promising Approach. SPE 155625 Presented at the SPE EOK Conference at Oil and Gas West Asia, Muscat, Oman. DOI: 10.2118/155625-MS (cit. on pp. 2,4, 8).
Zhang P. and Austad T. (2006). Wettability and Oil Recovery from Carbonates: Effects of Temperature and Potential Determining Ions. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 279 (1-3): pp. 179–187. DOI: 10.1016/j.colsurfa.2006.01.009 (cit. on pp. 2, 5, 8).
Zhang P., Tweheyo M. T., and Austad T. (2007a). Wettability Alteration and Improved Oil Recovery by Spontaneous Imbibition of Seawater into Chalk: Impact of the Potential Determining Ions Ca2+, Mg2+, and SO42-. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 301 (1-3): pp. 199–208. DOI: 10.1016/j.colsurfa.2006.12.058 (cit. on pp. 2, 5).
Zhang Y. and Morrow N. R. (2006). Comparison of Secondary and Tertiary Recovery with Change in Injection Brine Composition for Crude Oil/ Sandstone Combinations. SPE 99757 Presented at SPE/DOE Symposium on Improved Oil Kecovery, Tulsa, 22-26 April. DOI: 10.2523/99757-MS (cit. onp. 2).
Zhang Y., Xie X., and Morrow N. R. (2007b). Waterflood Performance by Injection of Brine with Different Salinity for Reservoir Cores. SPE Annual Technical Conference and Exhibition, 2: pp. 1217–1228. DOI: 10.2523/109849-MS (cit. on pp. 2, 8).