Electrokinetics of Carbonate/Brine Interface in Low-Salinity Waterflooding: Effect of Brine Salinity, Composition, Rock Type, and pH on ζ-Potential and a Surface-Complexation Model
- Hassan Mahani (Shell Global Solutions International B.V.) | Arsene Levy Keya (Shell Global Solutions International B.V.) | Steffen Berg (Shell Global Solutions International B.V.) | Ramez Nasralla (Shell Global Solutions International B.V.)
- Document ID
- Society of Petroleum Engineers
- SPE Journal
- Publication Date
- February 2017
- Document Type
- Journal Paper
- 53 - 68
- 2017.Society of Petroleum Engineers
- Carbonate rock, Low Salinity Waterflooding, Surface complexation modeling, Wettability modification, Electrokinetics
- 15 in the last 30 days
- 910 since 2007
- Show more detail
- View rights & permissions
|SPE Member Price:||USD 10.00|
|SPE Non-Member Price:||USD 30.00|
Laboratory studies have shown that wettability of carbonate rock can be altered to a less-oil-wetting state by manipulation of brine composition and reduction of salinity. Our recent study (Mahani et al. 2015b) suggests that surface-charge alteration is likely to be the driving mechanism of the low-salinity effect in carbonates. Various studies have already established the sensitivity of carbonate-surface charge to brine salinity, pH value, and potential-determining ions in brines. However, in the majority of the studies, single-salt brines or model-carbonate rocks have been used and it is fairly unclear how natural rock reacts to reservoir-relevant brine as well as successive brine dilution; whether different types of carbonate-reservoir rocks exhibit different electrokinetic properties; and how the surface-charge behavior obtained at different brine salinities and pH values can be explained.
This paper presents a comparative study aimed at gaining more insight into the electrokinetics of different types of carbonate rock. This is achieved by ζ-potential measurements on Iceland spar calcite and three reservoir-related rocks—Middle Eastern limestone, Stevns Klint chalk, and Silurian dolomite outcrop—over a wide range of salinity, brine composition, and pH values. With a view to arriving at a more-tractable approach, a surface-complexation model (SCM) implemented in PHREEQC software (Parkhurst and Appelo 2013) is developed to relate our understanding of the surface reactions to measured ζ-potentials.
It was found that regardless of the rock type, the trends of ζ-potentials with salinity and pH are quite similar. For all cases, the surface charge was found to be positive in high-salinity formation water (FW), which should favor oil-wetting. The ζ-potential successively decreased toward negative values when the brine salinity was lowered to seawater (SW) level and diluted SW. At all salinities, the ζ-potential showed a strong dependence on pH, with positive slope that remained so even with excessive dilution. The sensitivity of the ζ-potential to pH change was often higher at lower salinities.
The existing SCMs cannot predict the observed increase of ζ-potential with pH; therefore, a new model is proposed to capture this feature. According to modeling results, formation of surface species, particularly >CaSO–4 and to a lower extent >CO3Ca+ and >CO3Mg+, strongly influence the total surface charge. Increasing the pH turns the negatively charged moiety >CaSO–4 into both negatively charged >CaCO–3 and neutral >CaOH entities. (Note that throughout this paper, the symbol > indicates surface complexes.) This substitution reduces the negative charge of the surface. The surface concentration of >CO3Ca+ and >CO3Mg+ moieties changes little with change of pH.
Nevertheless, besides similarities in ζ-potential trends, there exist notable differences in terms of magnitude and the isoelectric point (IEP), even between carbonates that are mainly composed of calcite. Among all the samples, chalk particles exhibited the most negative surface charges, followed by limestone. In contrast to this, dolomite particles showed the most positive ζ-potential, followed by calcite crystal. Overall, chalk particles exhibited the highest surface reactivity to pH and salinity change, whereas dolomite particles showed the lowest.
|File Size||1 MB||Number of Pages||16|
Adamson, L. G., Chilingar, G. V. and Beeson, C. M. 1963. Some Data on Electrokinetic Phenomena and Their Possible Application in Petroleum Production. Chimika Chronika 28 (10): 121–127.
Al-Attar, H. H., Mahmoud, M. Y., Zekri, A. Y. et al. 2013. Low-Salinity Flooding in a Selected Carbonate Reservoir: Experimental Approach. J. Petrol. Explor. Prod. Technol. 3 (2): 139–149. http://dx.doi.org/10.1007/s13202-013-0052-3.
Al-Shalabi, E., Seperhrnoori, K. and Pope, G. 2015. Geochemical Interpretation of Low-Salinity Water Injection in Carbonate Oil Reservoirs. SPE J. 20 (6): 1212–1226. SPE-169101-PA. http://dx.doi.org/10.2118/169101-PA.
Alameri, W., Teklu, T. W., Graves, R. M. et al. 2014. Wettability Alteration During Low-Salinity Waterflooding in Carbonate Reservoir Cores. Presented at SPE Asia Pacific Oil & Gas Conference and Exhibition, Adelaide, Australia, 14–16 October. SPE-171529-MS. http://dx.doi.org/10.2118/171529-MS.
Alotaibi, M. B., Nasr-El-Din, H. A. and Fletcher, J. J. 2011. Electrokinetics of Limestone and Dolomite Rock Particles. SPE Res Eval & Eng 14 (5): 594–603. SPE-148701-PA. http://dx.doi.org/10.2118/148701-PA.
Alotaibi, M. B., Nasralla, R. A. and Nasr-EL-Din, H. A. 2010. Wettability Challenges in Carbonate Reservoirs. Presented at SPE Improved Oil Recovery Symposium, Tulsa, 24–28 April. SPE-129972-MS. http://dx.doi.org/10.2118/129972-MS.
Alroudhan, A. R., Vinogradov, J. and Jackson, M. D. 2015. Zeta Potential in Carbonates at Reservoir Conditions - Application to IOR. Oral presentation given at IOR 2015 – 18th European Symposium on Improved Oil Recovery, Dresden, Germany, 14–16 April.
Appelo, C. A. J. and Postma, D. 2005. Geochemistry, Groundwater and Pollution, second edition. Boca Raton, Florida: CRC Press.
Austad, T., Rezaeidoust, A. and Puntervold, T. 2010. Chemical Mechanism of Low Salinity Water Flooding in Sandstone Reservoirs. Presented at the SPE Improved Oil Recovery Symposium, Tulsa, 24–28 April. SPE-129767-MS. http://dx.doi.org/10.2118/129767-MS.
Austad, T., Shariatpanahi, S. F., Strand, S. et al. 2011. Conditions for a Low Salinity Enhanced Oil Recovery (EOR) Effect In Carbonate Oil Reservoirs. Energ. Fuel. 26 (1): 569–575. http://dx.doi.org/10.1021/ef201435g.
Austad, T., Strand, S., Høgnesen, E. J. et al. 2005. Seawater as IOR Fluid in Fractured Chalk. Presented at the SPE International Symposium on Oilfield Chemistry, The Woodlands, Texas, 2–4 February. SPE-93000-MS. http://dx.doi.org/10.2118/93000-MS.
Berg, S., Cense, A. W., Jansen, E. et al. 2010. Direct Experimental Evidence of Wettability Modification by Low Salinity. Petrophys. 51 (5): 314–322. SPWLA-2010-v51n5a3.
Boussour, S., Cissokho, M., Cordier, P. et al. 2009. Oil Recovery by Low Salinity Brine Injection: Laboratory Results on Outcrop and Reservoir Cores. Presented at the SPE Annual Technical Conference and Exhibition, New Orleans, 4–7 October. SPE-124277-MS. http://dx.doi.org/10.2118/124277-MS.
Brady, P. V. and Krumhansl, J. L. 2012. A Surface Complexation Model of Oil–Brine–Sandstone Interfaces at 100 _C: Low Salinity Waterflooding. J. Pet. Sci. Eng. 81 (January): 171–176. http://dx.doi.org/10.1016/j.petrol.2011.12.020.
Brady, P. V., Krumhansl, J. L. and Mariner, P. E. 2012. Surface Complexation Modeling for Improved Oil Recovery. Presented at the SPE Improved Oil Recovery Symposium, Tulsa, 14–18 April. SPE-153744-MS. http://dx.doi.org/10.2118/153744-MS.
Brunauer, S., Emmett, P. H. and Teller, E. 1938. Adsorption of Gases in Multimolecular Layers. Journal of the American Chemical Society 60 (2): 309–319. http://dx.doi.org/10.1021/ja01269a023.
Chandrasekhar, S. and Mohanty, K. K. 2013. Wettability Alteration with Brine Composition in High Temperature Carbonate Reservoirs. Presented at the SPE Annual Technical Conference and Exhibition, New Orleans, 30 September–2 October. SPE-166280-MS. http://dx.doi.org/10.2118/166280-MS.
Chen, L., Zhang, G., Wang, L. et al. 2014. Zeta Potential of Limestone in a Large Range of Salinity. Colloid. Surface. A 450: 1–8. https://doi.org/10.1016/j.colsurfa.2014.03.006.
Chilingar, G. and Haroun, M. 2015. Electrokinetics for Petroleum and Environmental Engineers. Hoboken, New Jersey: John Wiley & Sons.
Den Ouden, L., Nasralla, R. A., Guo, H. et al. 2015. Calcite Dissolution Behaviour During Low Salinity Water Flooding in Carbonate Rock. Oral presentation given at IOR 2015 – 18th European Symposium on Improved Oil Recovery, Dresden, Germany, 14–16 April.
Fathi, S. J., Austad, T. and Strand, S. 2012. Water-Based Enhanced Oil Recovery (EOR) by “Smart water” in Carbonate Reservoirs. Presented at the SPE EOR Conference at Oil and Gas West Asia, Muscat, Oman, 16–18 April. SPE-154570-MS. http://dx.doi.org/10.2118/154570-MS.
Fernø, M. A., Grønsdal, R., Åsheim, J. et al. 2011. Use of Sulfate for Water Based Enhanced Oil Recovery during Spontaneous Imbibition in Chalk. Energ. Fuel. 25 (4): 1697–1706. http://dx.doi.org/10.1021/ef200136w.
Gupta, R., Smith, P. G., Hu, L. et al. 2011. Enhanced Waterflood for Middle East Carbonate Cores – Impact of Injection Water Composition. Presented at the SPE Middle East Oil and Gas Show and Conference, Manama, Bahrain, 25–28 September. SPE-142668-MS. http://dx.doi.org/10.2118/142668-MS.
Hassenkam, T., Pedersen, C. S., Dalby, K. et al. 2011. Pore Scale Observation of Low Salinity Effects on Outcrop and Oil Reservoir Sandstone. Colloid. Surface. A 390 (1–3): 179–188. http://dx.doi.org/10.1016/j.colsurfa.2011.09.025.
Hiorth, A., Cathles, L. and Madland, M. 2010. The Impact of Pore Water Chemistry on Carbonate Surface Charge and Oil Wettability. Transport Porous Med. 85 (1): 1–21. http://dx.doi.org/10.1007/s11242-010-9543-6.
Hunter, R. J. 1981. Zeta-potentioal in Colloids Science. New York City: Academic Press.
Israelachivili, J. 1985. Intermolecular and Surface Forces. New York City: Academic Press.
Lager, A., Webb, K. J., Black, C. J. J. et al. 2008. Low Salinity Oil Recovery – An Experimental Investigation. Petrophys. 49 (1): 28–35. SPWLA-2008-v49n1a2.
Lee, S. Y., Webb, K. Y., Collins, I. R. et al. 2010. Low-Salinity Oil Recovery – Increasing Understanding of the Underlying Mechanisms. Presented at the SPE Improved Oil Recovery Symposium, Tulsa, 24–28 April. SPE-129722-MS. http://dx.doi.org/10.2118/129722-MS.
Ligthelm, D. J., Gronsveld, J., Hofman, J. P. et al. 2009. Novel Waterflooding Strategy by Manipulation of Injection Brine Composition. Presented at the EUROPEC/EAGE Conference and Exhibition, Amsterdam, 8–11 June. SPE-119835-MS. http://dx.doi.org/10.2118/119835-MS.
Mahani, H., Berg, S., Ilic, D. et al. 2015a. Kinetics of Low-Salinity-Flooding Effect. SPE J. 20 (1): 8–20. SPE-165255-PA. http://dx.doi.org/10.2118/165255-PA.
Mahani, H., Keya, A., Berg, S. et al. 2015b. Insights into the Mechanism of Wettability Alteration by Low Salinity Waterflooding (LSF) in Carbonates. Energ. Fuel. 29 (3): 1352–1367. http://dx.doi.org/10.1021/ef5023847.
Mahani, H., Sorop, T. G., Ligthelm, D. et al. 2011. Analysis of Field Responses to Low-Salinity Waterflooding in Secondary and Tertiary Mode in Syria. Presented at the SPE EUROPEC/EAGE Annual Conference and Exhibition, Vienna, Austria, 23–26 May. SPE-142960-MS. http://dx.doi.org/10.2118/142960-MS.
Marouf, R., Marouf-Khelifa, K., Schott, J. et al. 2009. Zeta Potential Study of Thermally Treated Dolomite Samples in Electrolyte Solutions. Micropor. Mesopor. Mat. 122 (1–3): 99–104. http://dx.doi.org/10.1016/j.micromeso.2009.02.021.
McGuire, P. L., Chatham, J. R., Paskvan, F. K. et al. 2005. Low Salinity Oil Recovery: An Exciting New EOR Opportunity for Alaska’s North Slope. Presented at SPE Western Regional Meeting, Irvine, California, 30 March–1 April. SPE-93903-MS. http://dx.doi.org/10.2118/93903-MS.
Mielczarski, J. A., Schott, J. and Pokrovsky, O. S. 2006. Surface Speciation of Dolomite and Calcite in Aqueous Solutions. In Encyclopedia of Surface and Colloid Science, second edition, ed. P. Somasundaran, 5965–5978. Boca Raton, Florida: CRC Press.
Moulin, P. and Roques, H. 2003. Zeta Potential Measurement of Calcium Carbonate. J. Colloid Interf. Sci. 261 (1): 115–126. http://dx.doi.org/10.1016/S0021-9797(03)00057-2.
Nasralla, R. A., Bataweel, M. A. and Nasr-El-Din, H. A. 2013. Investigation of Wettability Alteration and Oil-Recovery Improvement by Low-Salinity Water in Sandstone Rock. J Can Pet Technol 52 (2): 144–154. SPE-146322-PA. http://dx.doi.org/10.2118/146322-PA.
Nasralla, R. A., Sergienko, E., Masalmeh, S. M. et al. 2014. Demonstrating the Potential of Low-Salinity Waterflood to Improve Oil Recovery in Carbonate Reservoirs by Qualitative Coreflood. Presented at the Abu Dhabi International Petroleum Exhibition and Conference, Abu Dhabi, 10–13 November. SPE-172010-MS. http://dx.doi.org/10.2118/172010-MS.
Nasralla, R. A., Snippe, J. R. and Farajzadeh, R. 2015. Coupled Geochemical-Reservoir Model to Understand the Interaction between Low Salinity Brines and Carbonate Rock. Presented at the SPE Enhanced Oil Recovery Conference, Kuala Lumpur, 11–13 August. SPE-174661-MS. http://dx.doi.org/10.2118/174661-MS.
Okhrimenko, D., Dalby, K., Nicole, K. et al. 2013. Adsorption Properties of Chalk: Contributions from Calcite and Clays. Procedia Earth Planet. Sci. 7: 632–635. http://dx.doi.org/10.1016/j.proeps.2013.03.144.
Parkhurst, D. L. and Appelo, C. A. J. 2013. User Manual PHREEQC (Version 3)—A Computer Program for Speciation, Batch-Reaction, One-Dimensional Transport, and Inverse Geochemical Calculations. Denver: U.S. Geological Survey.
Pokrovsky, O. S., Schott, J. and Thomas, F. 1999. Dolomite Surface Speciation and Reactivity in Aquatic Systems. Geochim. Cosmochim. Ac. 63 (19–20): 3133–3143. http://dx.doi.org/10.1016/S0016-7037(99)00240-9.
Rezaei Gomari, K. A., Karoussi, O. and Hamouda, A. 2006. Mechanistic Study of Interaction Between Water and Carbonate Rocks for Enhancing Oil Recovery. Presented at SPE Europec/EAGE Annual Conference and Exhibition, Vienna, Austria. 12–15 June. SPE-99628-MS. http://dx.doi.org/10.2118/99628-MS.
Romanuka, J., Hofman, J., Ligthelm, D. J. et al. 2012. Low Salinity EOR in Carbonates. Presented at SPE Improved Oil Recovery Symposium, Tulsa, 14–18 April. SPE-153869-MS. http://dx.doi.org/10.2118/153869-MS.
Romero, M. I., Gamage, P., Jiang, H. et al. 2013. Study of Low-Salinity Waterflooding for Single- and Two- Phase Experiments in Berea Sandstone Cores. J. Pet. Sci. Eng. 110 (October): 149–154. http://dx.doi.org/10.1016/j.petrol.2013.08.050.
Shehata, A. M., Alotaibi, M. B. and Nasr-El-Din, H. A. 2014. Waterflooding in Carbonate Reservoirs: Does the Salinity Matter? SPE Res Eval & Eng 17 (3): 304–313. SPE-170254-PA. http://dx.doi.org/10.2118/170254-PA.
Stipp, S. L. and Hochella, M. F. Jr. 1991. Structure and Bonding Environments at the Calcite Surface Observed with X-ray Photoelectron Spectroscopy (XPS) and Low Energy Electron Diffraction (LEED). Geochim. Cosmochim. Ac. 55 (6): 1723–1736. http://dx.doi.org/10.1016/0016-7037(91)90142-R.
Strand, S., Høgnesen, E. J. and Austad, T. 2006. Wettability Alteration of Carbonates – Effects of Potential Determining Ions (Ca2+ and SO2_4 ) and Temperature. Colloid. Surface. A 275 (1–3): 1–10. http://dx.doi.org/10.1016/j.colsurfa.2005.10.061.
Tang, G. and Morrow, N. R. 1997. Salinity, Temperature, Oil Composition, and Oil Recovery by Waterflooding. SPE Res Eng 12 (4): 269–276. SPE-36680-PA. http://dx.doi.org/10.2118/36680-PA.
Van Cappellen, P., Charlet, L., Stumm, W. et al. 1993. A Surface Complexation Model of the Carbonate Mineral-Aqueous Solution Interface. Geochim. Cosmochim. Ac. 57 (15): 3505–3518. http://dx.doi.org/10.1016/0016-7037(93)90135-J.
Vledder, P., Fonseca, J. C., Wells, T. et al. 2010. Low Salinity Flooding: Proof of Wettability Alteration on a Field Wide Scale. Presented at the SPE Improved Oil Recovery Symposium, Tulsa, 24–28 April. SPE-129564-MS. http://dx.doi.org/10.2118/129564-MS.
Webb, K. J., Black, C. J. J. and Tjetland, G. 2005. A Laboratory Study Investigating Methods for Improved Oil Recovery in Carbonates. Oral presentation given at the International Petroleum Technology Conference, Doha, 21–23 November.
Wolthers, M., Charlet, L. and Van Cappelen, 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. Am. J. Sci. 308 (8): 905–941. http://dx.doi.org/10.2475/08.2008.02.
Yi, Z. and Sarma, H. K. 2012. Improving Waterflood Recovery Efficiency in Carbonate Reservoirs through Salinity Variations and Ionic Exchanges: A Promising Low-Cost “Smart-Waterflood” Approach. Presented at the Abu Dhabi International Petroleum Conference and Exhibition, Abu Dhabi, 11–14 November. SPE-161631-MS. http://dx.doi.org/10.2118/161631-MS.
Yousef, A. A., Al-Saleh, S. and Al-Jawfi, M. S. 2012. Improved/Enhanced Oil Recovery from Carbonate Reservoirs by Tuning Injection Water Salinity and Ionic Content. Presented at the SPE Improved Oil Recovery Symposium, Tulsa, 14–18 April. SPE-154076-MS. http://dx.doi.org/10.2118/154076-MS.
Yousef, A. A., Al-Saleh, S., A-Kaabi, A. et al. 2011. Laboratory Investigation of the Impact of Injection-Water Salinity and Ionic Content on Oil Recovery from Carbonate Reservoirs. SPE Res Eval & Eng 14 (5): 578–593. SPE-137634-PA. http://dx.doi.org/10.2118/137634-PA.
Zahid, A., Shapiro, A. and Skauge, A. 2012. Experimental Studies of Low Salinity Water Flooding in Carbonate Reservoirs: A New Promising Approach. Presented at the SPE EOR Conference at Oil and Gas West Asia, Muscat, Oman, 16–18 April. SPE-155625-MS. http://dx.doi.org/10.2118/155625-MS.
Zaretskiy, Y. 2012. Towards Modelling Physical and Chemical Effects during Wettability Alteration in Carbonates at Pore and Continuum Scales. PhD dissertation, Herriot-Watt University, Edinburgh, Scotland, May 2012.
Zhang, P. and Austad, T. 2006. Wettability and Oil Recovery from Carbonates: Effects of Temperature and Potential Determining Ions. Colloid. Surface. A 279 (1–3): 179–187. http://dx.doi.org/10.1016/j.colsurfa.2006.01.009.
Zhang, P., Tweheyo, M. T. and Austad, T. 2007. Wettability Alteration and Improved Oil Recovery by Spontaneous Imbibition of Seawater in Chalk: Impact of Potential Determining Ions Ca2+, Mg2+, and SO2_4. Colloid. Surface. A 301 (1–3): 199–208. http://dx.doi.org/10.1016/j.colsurfa.2006.12.058.
Zhang, Y. and Morrow, N. R. 2006. Comparison of Secondary and Tertiary Recovery with Change in Injection Brine Composition for Crude Oil/Sandstone Combinations. Presented at the SPE/DOE Symposium on Improved Oil Recovery, Tulsa, 22–26 April. SPE-99757-MS. http://dx.doi.org/10.2118/99757-MS.