The Effect of pH and Mineralogy on the Retention of Polymeric Scale Inhibitors on Carbonate Rocks for Application in Squeeze Treatments
- Khosro Jarrahian (Heriot-Watt University) | Ken S. Sorbie (Heriot-Watt University) | Michael A. Singleton (Heriot-Watt University) | Lorraine S. Boak (Heriot-Watt University) | Alexander J. Graham (Heriot-Watt University)
- Document ID
- Society of Petroleum Engineers
- SPE Production & Operations
- Publication Date
- May 2019
- Document Type
- Journal Paper
- 344 - 360
- 2019.Society of Petroleum Engineers
- Scale Inhibitor Retention, Squeeze Treatments, Polymeric Scale Inhibitors, Carbonate Formations
- 2 in the last 30 days
- 195 since 2007
- Show more detail
- View rights & permissions
|SPE Member Price:||USD 5.00|
|SPE Non-Member Price:||USD 35.00|
The bulk “apparent-adsorption” behavior (Γapp vs. Cf) of two polymeric scale inhibitors (SIs), polyphosphino carboxylic acid (PPCA) and phosphorus-functionalized copolymer (PFC), onto carbonate mineral substrates has been studied for initial solution pH values of 2, 4, and 6. The two carbonate minerals used, calcite and dolomite, are much more chemically reactive than sandstone minerals (such as quartz, feldspars, and clays), which have already been studied extensively. In nearly all cases, precipitates formed at higher SI concentrations were caused by the formation of sparingly soluble SI/calcium (Ca) complexes. A systematic study has been performed on the SI/Ca precipitates formed by applying both environmental scanning electron microscopy energy-dispersive X-ray (ESEM-EDX) analysis and particle-size analysis (PSA), and this identifies the morphology and the approximate composition of the precipitates.
For PPCA, at all initial solution pH values, regions of pure adsorption (Γ) (PPCA < 100 ppm) and coupled adsorption/precipitation (Γ/Π) are clearly observed for both calcite and dolomite. PFC at pH values of 4 and 6 also showed very similar behavior, with a region of pure adsorption (Γ) for PFC < 500 ppm and a region of coupled adsorption/precipitation (Γ/Π) above this level. However, the PFC/calcite case at pH = 2 showed only pure adsorption, whereas the PFC/dolomite case at pH = 2 again showed coupled adsorption/precipitation at higher PFC concentrations. For the SIs on both carbonate substrates, precipitation is the more dominant mechanism for SI retention than adsorption above a minimum concentration of approximately 100 to 500 ppm SI. The actual amount of precipitate formed varies from case to case, depending on the specific SI, the substrate (calcite/dolomite), and the initial pH (pH = 2, 4, and 6).
Although the qualitative behaviors of both PPCA and PFC were similar on both carbonate substrates, the apparent adsorption of PPCA was higher on calcite than on dolomite, and the apparent adsorption of PFC was higher on dolomite than on calcite. We discuss here how these observations are related to the reactivity of the different carbonate minerals, the resulting final pH (which affects the dissociation of the SI), the Ca-SI binding, and the solubility of the resulting complex.
|File Size||1 MB||Number of Pages||17|
Baraka-Lokmane, S. and Sorbie, K. S. 2004. Scale Inhibitor Core Floods in Carbonate Cores: The Influence of pH on Phosphonate-Carbonate Interactions. Presented at the SPE International Symposium on Oilfield Scale, Aberdeen, 26–27 May. SPE-87448-MS. https://doi.org/10.2118/87448-MS.
Baraka-Lokmane, S. and Sorbie, K. S. 2006. Scale Inhibitor Core Floods in Carbonate Cores: Chemical Interactions and Modeling. Presented at the SPE International Oilfield Scale Symposium, Aberdeen, 31 May–1 June. SPE-100515-MS. https://doi.org/10.2118/100515-MS.
Farooqui, N. M. 2015. A Detailed Study of the Scale Inhibitor Phase Envelope of PPCA in the Context of Precipitation Squeeze Treatments. PhD dissertation, Heriot-Watt University, Edinburgh, Scotland (May 2015).
Fleming, N., Bourne, H. M., Strachan, C. J. et al. 2001. Development of an Ecofriendly Scale Inhibitor for Harsh Scaling Environments. Presented at the SPE International Symposium on Oilfield Chemistry, Houston, 13–16 February. SPE-65040-MS. https://doi.org/10.2118/65040-MS.
Ibrahim, J. M., Sorbie, K., and Boak, L. S. 2012. Coupled Adsorption/Precipitation Experiments: 1. Static Results. Presented at the SPE International Conference on Oilfield Scale, Aberdeen, 30–31 May. SPE-155109-MS. https://doi.org/10.2118/155109-MS.
Jordan, M. M. and Sorbie, K. S. 1994. The Effects of Clay Minerals, pH, Calcium and Temperature on the Adsorption of Phosphonate Scale Inhibitors Onto Reservoir Core and Mineral Separates. Presented at the NACE Annual Corrosion Conference, Baltimore, Maryland, 27 February–4 March.
Kahrwad, M., Sorbie, K. S., and Boak, L. S. 2008. Coupled Adsorption/Precipitation of Scale Inhibitors: Experiment Results and Modeling. Presented at the SPE International Oilfield Scale Conference, Aberdeen, 28–29 May. SPE-114108-MS. https://doi.org/10.2118/114108-MS.
Kan, A. T., Fu, G., Tomson, M. B. et al. 2004. Factors Affecting Scale Inhibitor Retention in Carbonate-Rich Formation During Squeeze Treatment. SPE J. 9 (3): 280–289. SPE-80230-PA. https://doi.org/10.2118/80230-PA.
Kan, A. T., Fu, G., and Tomson, M. B. 2005. Adsorption and Precipitation of an Aminoalkylphosphonate Onto Calcite. J. Colloid Interf. Sci. 281 (2): 275–284. https://doi.org/10.1016/j.jcis.2004.08.054.
Kerr, J. R., Goulding, J., and Sorbie, K. S. 2013. The Development and Application of Techniques for the Detailed Characterization of a Novel Series of Functionalized Polymeric Scale Inhibitors. Presented at the SPE International Symposium on Oilfield Chemistry, The Woodlands, Texas, 8–10 April. SPE-164124-MS. https://doi.org/10.2118/164124-MS.
Malvern Instruments is a registered trademark of Malvern Panalytical Limited, Worcestershire, United Kingdom.
Meyers, K. O., Skillman, H. L., and Herring, G. D. 1985. Control of Formation Damage at Prudhoe Bay, Alaska, by Inhibitor Squeeze Treatment. J Pet Technol 37 (6): 1019–1034. SPE-12472-PA. https://doi.org/10.2118/12472-PA.
Park, W. K., Ko, S.-J., Lee, S. W. et al. 2008. Effects of Magnesium Chloride and Organic Additives on the Synthesis of Aragonite Precipitated Calcium Carbonate. J. Cryst. Growth 310 (10): 2593–2601. https://doi.org/10.1016/j.jcrysgro.2008.01.023.
Pokrovsky, S. O., Golubev, S. V., and Schott, J. 2005. Dissolution Kinetics of Calcite, Dolomite and Magnesite at 25°C and 0 to 50 atm pCO2. Chem. Geol. 217 (3–4): 239–255. https://doi.org/10.1016/j.chemgeo.2004.12.012.
Shaw, S. S. 2012. Investigation Into the Mechanisms of Formation and Prevention of Barium Sulphate Oilfield Scale. PhD dissertation, Heriot-Watt University, Edinburgh, Scotland (May 2012).
Singleton, M. A., Collins, J. A., Poynton, N. et al. 2000. Developments in PhosphonoMethylated PolyAmine (PMPA) Scale Inhibitor Chemistry for Severe BaSO Scaling Conditions. Presented at the International Symposium on Oilfield Scale, Aberdeen, 26–27 January. SPE-60216-MS. https://doi.org/10.2118/60216-MS.
Sorbie, K. S. and Gdanski, R. D. 2005. A Complete Theory of Scale Inhibitor Transport, Adsorption/Desorption and Precipitation in Squeeze Treatments. Presented at the SPE International Symposium on Oilfield Scale, Aberdeen, 11–12 May. SPE-95088-MS. https://doi.org/10.2118/95088-MS.
Sorbie, K. S., Wat, R. M. S., and Todd, A. C. 1992. Interpretation and Theoretical Modeling of Scale Inhibitor/Tracer Corefloods. SPE Prod Eng 7 (3): 307–312. SPE-20687-PA. https://doi.org/10.2118/20687-PA.
Sutherland, L. and Jordan, M. 2016. Enhancing Scale Inhibitor Squeeze Retention With Additives. Presented at the SPE International Oilfield Scale Conference and Exhibition, Aberdeen, 11–12 May. SPE-179888-MS. https://doi.org/10.2118/179888-MS.
Thomas, W. S., Sorbie, K. S., and Singleton, M. A. 2014. Coupled Adsorption/Precipitation Tests With a Phosphonate Inhibitor and Carbonate Substrate. Presented at the SPE International Oilfield Scale Conference and Exhibition, Aberdeen, 14–15 May. SPE-169779-MS. https://doi.org/10.2118/169779-MS.
Todd, M. J., Strachan, C. J., Moir, G. et al. 2010. Development of the Next Generation of Phosphorus Tagged Polymeric Scale Inhibitors. Presented at the SPE International Conference on Oilfield Scale, Aberdeen, 26–27 May. SPE-130733-MS. https://doi.org/10.2118/130733-MS.
Tomson, M. B., Kan, A. T., and Fu, G. 2004. Control of Inhibitor Squeeze via Mechanistic Understanding of Inhibitor Chemistry. Presented at the SPE International Symposium on Oilfield Scale, Aberdeen, 26–27 May. SPE-87450-MS. https://doi.org/10.2118/87450-MS.
Tomson, M. B., Kan, A. T., Fu, G. et al. 2008. Mechanistic Understanding of Rock/Phosphonate Interactions and Effect of Metal Ions on Inhibitor Retention. SPE J. 13 (3): 325–336. SPE-100494-PA. https://doi.org/10.2118/100494-PA.
Wang, C., Li, S.-P., and Li, T.-D. 2008. Calcium Carbonate Inhibition by a Phosphonate-Terminated Poly(Maleic-Co-Sulfonate) Polymeric Inhibitor. Desalination 249 (1): 1–4. https://doi.org/10.1016/j.desal.2009.06.006.