A Mechanistic Understanding of Asphaltenes Precipitation From Varying-Saturate-Concentration Perspectives
- Andreas A. Prakoso (Texas A&M University) | Abhishek D. Punase (Texas A&M University) | Berna Hascakir (Texas A&M University)
- Document ID
- Society of Petroleum Engineers
- SPE Production & Operations
- Publication Date
- February 2017
- Document Type
- Journal Paper
- 86 - 98
- 2017.Society of Petroleum Engineers
- SARA fractionation, Asphaltene Precipitation, Saturates
- 4 in the last 30 days
- 333 since 2007
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Asphaltenes precipitation within reservoir pores or production flowlines can severely hamper the petroleum-extraction process. Although the effect of temperature and pressure on asphaltene deposition is well-known, the manner in which the variations in oil composition affect the asphaltenes-precipitation mechanism requires more clarity. This work investigates the effect of crude-oil compositional change on asphaltene stability. The impact of oil composition is analyzed by preparing pseudocomponents through blending the crude oil with their own saturates fractions.
A systematic characterization of 11 different bitumen and crude-oil samples was carried out by density and viscosity measurements and the determination of the elemental composition and saturates, aromatics, resins, and asphaltenes (SARA) contents. Further analyses were conducted on the asphaltenes separated by use of n-pentane. The cluster size was determined by a particle-size analyzer, and the stability of asphaltenes was evaluated by zeta-potential. The molecular structure of SARA fractions and bulk crude-oil samples was analyzed by Fourier-transform infrared (FTIR) spectroscopy. Onset-of-asphaltenes-precipitation (OAP) tests on crude-oil samples were achieved by the addition of different solvents (n-pentane, n-heptane, and crude-oil saturates fraction).
While the physical characterization studies could only provide weak relations between the density/viscosity and the asphaltene content of the bulk samples, it has been found that mainly the ratio of the heavy (resins+asphaltenes) to light (saturates+aromatics) fractions controls the viscosity and the °API value of the crude oils. As this ratio increases, the crude oil becomes more viscous and dense. Also, the asphaltene/resin ratio was found to be critical because of its impact on asphaltene stability, which was determined through zeta-potential measurements. The high asphaltene/resin ratios result in low asphaltene stability; however, this effect is surpassed by the higher aromatics fraction in the bulk oil. Asphaltene stability was further studied with OAP tests. The OAP-test results provide the behavior of asphaltenes after the interaction of bulk oil samples with normal saturated hydrocarbons; however, our study improves the OAP-test procedure by conducting OAP tests with crude oil’s own saturates fractions. The interaction of saturates fraction with crude oil resulted in more asphaltenes precipitation compared with interaction of n-pentane and n-heptane. The FTIR analyses indicate the presence of impurities in saturates fractions, and these impurities are believed to cause higher asphaltenes precipitation as a result of the polar nature of the impurities.
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Akbarzadeh, K., Alboudwarej, H., Svrcek, W. Y. et al. 2005. A Generalized Regular Solution Model for Asphaltene Precipitation From n-Alkane Diluted Heavy Oils and Bitumens. Fluid Phase Equilibria 232 (1–2): 159–170. http://dx.doi.org/10.1016/j.fluid.2005.03.029.
Akbarzadeh, K., Hammami, A., Kharrat, A. et al. 2007. Asphaltenes—Problematic but Rich in Potential. Oilfield Review, 22–43. https://www.slb.com/~/media/Files/resources/oilfield_review/ors07/sum07/p22_43.pdf.
ASTM D2007-11, Standard Test Method for Characteristic Groups in Rubber Extender and Processing Oils and Other Petroleum-Derived Oils by the Clay-Gel Absorption Chromatographic Method. 2011. West Conshohocken, Pennsylvania: ASTM International. http://dx.doi.org/10.1520/D2007-11.
ASTM D3279-12e1, Standard Test Method for n-Heptane Insolubles. 2012. West Conshohocken, Pennsylvania: ASTM International. http://dx.doi.org/10.1520/D3279-12E01.
Beck, J., Svrcek, W. Y., and Yarranton, H. W. 2005. Hysteresis in Asphaltene Precipitation and Redissolution. Energy Fuels 19 (3): 944–947. http://dx.doi.org/10.1021/ef049707n.
Becker, H. L. Jr. 2000. Asphaltene: To Treat or Not. Presented at the SPE Permian Basin Oil and Gas Recovery Conference, Midland, Texas, USA, 21–23 March. SPE-59703-MS. http://dx.doi.org/10.2118/59703-MS.
Bellamy, L. J. 1980. The Infrared Spectra of Complex Modules: Advances in Infrared Group Frequencies, Vol. 2. London: Springer (Reprint).
Bertaux, J., Fröhlich, F., and Ildefonse, P. 1998. Multicomponent Analysis of FTIR Spectra: Quantification of Amorphous and Crystallized Mineral Phases in Synthetic and Natural Sediments. Journal of Sedimentary Research 68 (3): 440–447.
Bishop, J. L., Koeberl, C., Kralik, C. et al. 1996. Reflectance Spectroscopy and Geochemical Analyses of Lake Hoare Sediments, Antarctica: Implications for Remote Sensing of the Earth and Mars. Geochimica et Cosmochimica Acta 60 (5): 765–785. http://dx.doi.org/10.1016/0016-7037(95)00432-7.
Buenrostro-Gonzalez, E., Lira-Galeana, C., Gil-Villegas, A. et al. 2004. Asphaltene Precipitation in Crude Oils: Theory and Experiments. AIChE Journal 50 (10): 2552–2570. http://dx.doi.org/10.1002/aic.10243.
Carnahan, N. F., Salager, J-L., Antón, R. et al. 1999. Properties of Resins Extracted From Boscan Crude Oial and Their Effect on the Stability of Asphaltenes in Boscan and Hamaca Crude Oils. Energy Fuels 13 (2): 309–314. http://dx.doi.org/10.1021/ef980218v.
Castro, L. V. and Vazquez, F. 2009. Fractionation and Characterization of Mexican Crude Oils. Energy Fuels 23 (3): 1603–1609. http://dx.doi.org/10.1021/ef8008508.
Cenegy, L. M. 2001. Survey of Successful World-Wide Asphaltene Inhibitor Treatments in Oil Production Fields. Presented at the SPE Annual Technical Conference and Exhibition, New Orleans, 30 September–3 October. SPE-71542-MS. http://dx.doi.org/10.2118/71542-MS.
Clayden, J. 2001. Organic Chemistry. Oxford: Oxford University Press (Reprint).
da Silva Ramos, A. C., Haraguchi, L., Notrispe, F. R. et al. 2001. Interfacial and Colloidal Behavior of Asphaltenes Obtained From Brazilian Crude Oils. Journal of Petroleum Science and Engineering 32 (2–4): 201–216. http://dx.doi.org/10.1016/S0920-4105(01)00162-0.
Dusseault, M. B. 2001. Comparing Venezuelan and Canadian Heavy Oil and Tar Sands. Presented at the Canadian International Petroleum Conference, Calgary, 12–14 June. PETSOC-2001-061. http://dx.doi.org/10.2118/2001-061.
Fan, T. and Buckley, J. S. 2002. Rapid and Accurate SARA Analysis of Medium Gravity Crude Oils. Energy Fuels 16 (6): 1571–1575. http://dx.doi.org/10.1021/ef0201228.
Filby, R. H. and Branthaver, J. F. (eds.) 1987. Metal Complexes in Fossil Fuels: Geochemistry, Characterization, and Processing. Symposium Series Number 344. Washington, DC: American Chemical Society.
Freeman, D. E. and Hamble, A. N. 1957. Spectra of Sulphonyl Derivatives. III. Interaction With Attached Groups. Australian Journal of Chemistry 10 (3): 227–238.
Fuhr, B. J., Holloway, L. R., and Hammami, A. 1999. Analytical Considerations Related to Asphaltenes and Waxes in the Same Crudes. Energy Fuels 13 (2): 336–339. http://dx.doi.org/10.1021/ef980205h.
Gabrienko, A. A., Subramani, V., Martyanov, O. N. et al. 2014. Correlation Between Asphaltene Stability in n-Heptane and Crude Oil Composition Revealed With In Situ Chemical Imaging. Adsorption Science & Technology 32 (4): 243–255. http://dx.doi.org/10.1260/0263-6220.127.116.11.
Gaspar, A., Zellermann, E., Lababidi, S. et al. 2012. Characterization of Saturates, Aromatics, Resins, and Asphaltenes Heavy Crude Oil Fractions by Atmospheric Pressure Laser Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Energy Fuels 26 (6): 3481–3487. http://dx.doi.org/10.1021/ef3001407.
Goual, L. and Firoozabadi, A. 2002. Measuring Asphaltenes and Resins, and Dipole Moment in Petroleum Fluids. AIChE Journal 48 (11): 2646–2663. http://dx.doi.org/10.1002/aic.690481124.
Hammami, A., Phelps, C. H., Monger-McClure, T. et al. 2000. Asphaltene Precipitation From Live Oils: An Experimental Investigation of Onset Conditions and Reversibility. Energy Fuels 14 (1): 14–18. http://dx.doi.org/10.1021/ef990104z.
Hannisdal, A., Ese, M., Hemmingsen, P. V. et al. 2006. Particle-Stabilized Emulsions: Effect of Heavy Crude Oil Components Pre-Adsorbed Onto Stabilizing Solids. Colloids and Surfaces A: Physicochemical and Engineering Aspects 276 (1–3): 45–58. http://dx.doi.org/10.1016/j.colsurfa.2005.10.011.
He, L., Li, X., Wu, G. et al. 2013. Distribution of Saturates, Aromatics, Resins, and Asphaltenes Fractions in the Bituminous Layer of Athabasca Oil Sands. Energy Fuels 27 (8): 4677–4683. http://dx.doi.org/10.1021/ef400965m.
Jada, A. and Salou, M. 2002. Effects of the Asphaltene and Resin Contents of the Bitumens on the Water–Bitumen Interface Properties. Journal of Petroleum Science and Engineering 33 (1–3): 185–193. http://dx.doi.org/10.1016/S0920-4105(01)00185-1.
Kar, T. and Hascakir, B. 2015. The Role of Resins, Asphaltenes, and Water in Water–Oil Emulsion Breaking With Microwave Heating. Energy Fuels 29 (6): 3684–3690. http://dx.doi.org/10.1021/acs.energyfuels.5b00662.
Kar, T., Williamson, M., and Hascakir, B. 2014. The Role of Asphaltenes in Emulsions Formation for Steam Assisted Gravity Drainage (SAGD) and Expanding Solvent-SAGD (ES-SAGD). Presented at the SPE Heavy and Extra Heavy Oil Conference: Latin America, Medellin, Colombia, 24–26 September. SPE-171076-MS. http://dx.doi.org/10.2118/171076-MS.
Kar, T., Yeoh, J. J., Ovalles, C. et al. 2015. The Impact of Asphaltene Precipitation and Clay Migration on Wettability Alteration for Steam Assisted Gravity Drainage (SAGD) and Expanding Solvent-SAGD (ES-SAGD). Presented at the SPE Canada Heavy Oil Technical Conference, Calgary, Alberta, Canada. SPE-174439-MS. http://dx.doi.org/10.2118/174439-MS.
Kharrat, A. M., Zacharia, J., Cherian, V. J. et al. 2007. Issues With Comparing SARA Methodologies. Energy Fuels 21 (6): 3618–3621. http://dx.doi.org/10.1021/ef700393a.
Kokal, S. L. and Sayegh, S. G. 1995. Asphaltenes: The Cholesterol of Petroleum. Presented at the SPE Middle East Oil Show, Bahrain, 11–14 March. SPE-29787-MS. http://dx.doi.org/10.2118/29787-MS.
Krump, H., Alexy, P., and Luyt, A. S. 2005. Preparation of a Maleated Fischer-Tropsch Paraffin Wax and FTIR Analysis of Grafted Maleic Anhydride. Polymer Testing 24 (2): 129–135. http://dx.doi.org/10.1016/j.polymertesting.2004.09.011.
Leontaritis, K. J. 1989. Asphaltene Deposition: A Comprehensive Description of Problem Manifestations and Modeling Approaches. Presented at the SPE Production Operations Symposium, Oklahoma City, Oklahoma, 13–14 March. SPE-18892-MS. http://dx.doi.org/10.2118/18892-MS.
Lian, H., Lin, J., and Yen, T. F. 1994. Peptization Studies of Asphaltene and Solubilty Parameter Spectra. Fuel 73 (3): 423–428. http://dx.doi.org/10.1016/0016-2361(94)90097-3.
Liu, J., Zhou, Z., Xu, Z. et al. 2002. Bitumen–Clay Interactions in Aqueous Media Studied by Zeta Potential Distribution Measurement. J Colloid Interface Sci 252 (2): 409–418. http://dx.doi.org/10.1006/jcis.2002.8471.
Liu, P., Shi, Q., Chung, K. H. et al. 2010. Molecular Characterization of Sulfur Compounds in Venezuela Crude Oil and Its SARA Fractions by Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Energy & Fuels 24 (9): 5089–5096. http://dx.doi.org/10.1021/ef100904k.
Loeber, L., Muller, G., Morel, J. et al. 1998. Bitumen in Colloid Science: A Chemical, Structural and Rheological Approach. Fuel 77 (13): 1443–1450. http://dx.doi.org/10.1016/S0016-2361(98)00054-4.
Luo, P., Wang, X., and Gu, Y. 2010. Characterization of Asphaltenes Precipitated With Three Light Alkanes Under Different Experimental Conditions. Fluid Phase Equilibria 291 (2): 103–110. http://dx.doi.org/10.1016/j.fluid.2009.12.010.
Manual of Petroleum Measurement Standards, Chapter 11—Physical Properties Data, Section 1—Temperature and Pressure Volume Correction Factors for Generalized Crude Oils, Refined Products, and Lubricating Oils (adjunct to ASTM D 1250-04 and IP 200/04). 2004. Washington, DC: American Petroleum Institute.
McCain, W. D. Jr. 1990. The Properties of Petroleum Fluids, 2nd edition. Tulsa: PennWell Publishing Company (Reprint).
Meyer, R. F. Jr. and de Witt, W. 1990. Definition and World Resources of Natural Bitumens. U.S. Geological Survey Bulletin 1944, Department of the Interior, U.S. Geological Survey, Denver, Colorado, USA (Reprint).
Mitchell, D. L. and Speight, J. G. 1973. The Solubility of Asphaltenes in Hydrocarbon Solvents. Fuel 52 (2): 149–152. http://dx.doi.org/10.1016/0016-2361(73)90040-9.
Mózes, G. Y. 1984. Developments in Petroleum Science: Paraffin Products—Properties, Technologies, Applications, Vol. 14, 3–335. New York: Elsevier.
Mukhametshina, A., Kar, T., and Hascakir, B. 2016. Asphaltene Precipitation During Bitumen Extraction With Expanding Solvent Steam-Assisted Gravity Drainage: Effects on Pore-Scale Displacement. SPE J. 21 (2): 380–392. SPE-170013-PA. http://dx.doi.org/10.2118/170013-PA.
Mullins, O. C. 2010. The Modified Yen Model. Energy Fuels 24 (4): 2179–2207. http://dx.doi.org/10.1021/ef900975e.
Mullins, O. C. 2011. The Asphaltenes. Annu Rev Anal Chem 4: 393–418. http://dx.doi.org/10.1146/annurev-anchem-061010-113849.
Mullins, O. C., Betancourt, S. S., Cribbs, M. E. et al. 2007. The Colloidal Structure of Crude Oil and the Structure of Oil Reservoirs. Energy Fuels 21 (5): 2785–2794. http://dx.doi.org/10.1021/ef0700883.
Mullins, O. C., Seifert, D. J., Zuo, J. Y. et al. 2013. Clusters of Asphaltene Nanoaggregates Observed in Oilfield Reservoirs. Energy Fuels 27 (4): 1752–1761. http://dx.doi.org/10.1021/ef301338q.
Musser, B. J. and Kilpatrick, P. K. 1998. Molecular Characterization of Wax Isolated From a Variety of Crude Oils. Energy Fuels 12 (4): 715–725. http://dx.doi.org/10.1021/ef970206u.
Nalwaya, V., Tantayakom, V., Piumsomboon, P. et al. 1999. Studies on Asphaltenes Through Analysis of Polar Fractions. Ind. Eng. Chem. Res. 38 (3): 964–972. http://dx.doi.org/10.1021/ie9804428.
Nellensteyn, F. J. 1928. Relation of the Micelle to the Medium in Asphalt. Institue of Petroleum Technology 14: 134-138.
Osjord, E. H., Rønningsen, H. P., and Tau, L. 1985. Distribution of Weight, Density, and Molecular Weight in Crude Oil Derived From Computerized Capillary GC Analysis. Journal of Separation Science (10): 683–690. http://dx.doi.org/10.1002/jhrc.1240081008.
Parra-Barraza, H., Hernández-Montiel, D., Lizardi, J. et al. 2003. The Zeta Potential and Surface Properties of Asphaltenes Obtained With Different Crude Oil/n-Heptane Proportions. Fuel 82 (8): 869–874. http://dx.doi.org/10.1016/S0016-2361(03)00002-4.
Pereira, J. C., Delgado-Linares, J., Briones, A. et al. 2011. The Effect of Solvent Nature and Dispersant Performance on Asphaltene Precipitation From Diluted Solutions of Instable Crude Oil. Petroleum Science and Technology 29: 2432–2440. http://dx.doi.org/10.1080/10916461003735061.
Pfeiffer, J. Ph. and Saal, R. N. J. 1940. Asphaltic Bitumen as Colloid System. Journal of Physical Chemistry 44 (2): 139–149. http://dx.doi.org/10.1021/j150398a001.
Rappoport, Z. 2003. The Chemistry of Phenols. Chichester, England: Wiley (Reprint).
Ratajczak, H. 1972. Charge-Transfer Properties of the Hydrogen Bond. I. Theory of the Enhancement of Dipole Moment of Hydrogen-Bonded Systems. J. Phys. Chem. 76 (21): 3000–3004. http://dx.doi.org/10.1021/j100665a013.
Redelius, P. and Soenen, H. 2015. Relation Between Bitumen Chemistry and Performance. Fuel 140: 34–43. http://dx.doi.org/10.1016/j.fuel.2014.09.044.
Reichardt, C. 1988. Solvents and Solvent Effects in Organic Chemistry. Weinheim, Federal Republic of Germany: VCH (Reprint).
Riddick, T. 1968. Control of Colloid Stability Through Zeta Potential With a Closing Chapter on Its Relationship to Cardiovascular Disease. Wynnewood, Pennsylvania: Zeta-Meter Inc. (Reprint).
Rogel, E., Ovalles, C., and Moir, M. 2012. Asphaltene Chemical Characterization as a Function of Solubility: Effects on Stability and Aggregation. Energy Fuels 26 (5): 2655–2662. http://dx.doi.org/10.1021/ef2013979.
Sirota, E. B. 2005. Physical Structure of Asphaltenes. Energy Fuels 19 (4): 1290–1296. http://dx.doi.org/10.1021/ef049795b.
Skoog, D. A., West, D. M., Holler, F. J. et al. 2014. Fundamentals of Analytical Chemistry, ninth edition. Belmont, California: Brooks/Cole, Cengage Learning (Reprint).
Soenen, H. and Redelius, P. 2014. The Effect of Aromatic Interactions on the Elasticity of Bituminous Binders. Rheol Acta 53 (9): 741–754. http://dx.doi.org/10.1007/s00397-014-0792-0.
Speight, J. G. 2006. The Chemistry and Technology of Petroleum. New York City: CRC Press (Reprint).
Speight, J. G., Long, R. B., and Trowbridge, T. D. 1984. Factors Influencing the Separation of Asphaltenes From Heavy Petroleum Feedstocks. Fuel 63 (5): 616–620. http://dx.doi.org/10.1016/0016-2361(84)90156-X.
Spiecker, P. M., Gawrys, K. L., Trail, C. B. et al. 2003. Effects of Petroleum Resins on Asphaltene Aggregation and Water-In-Oil Emulsion Formation. Colloids and Surfaces A: Physicochem. Eng. Aspects 220 (1–3): 9–27. http://dx.doi.org/10.1016/S0927-7757(03)00079-7.
Taylor, S. E. 1998. The Electrodeposition of Asphaltenes and Implications for Asphaltene Structure and Stability in Crude and Residual Oils. Fuel 77 (8): 821–828. http://dx.doi.org/10.1016/S0016-2361(97)00271-8.
van der Marel, H. W. and Beutelspacher, H. 1976. Atlas of Infrared Spectroscopy of Clay Minerals and Their Admixtures. Amsterdam: Elsevier.
Waldo, G. S., Carlson, R. M. K., Moldowan, J. M. et al. 1991. Sulfur Speciation in Heavy Petroleums: Information From X-ray Absorption Near-Edge Structure. Geochimica et Cosmochimica Acta 55 (3): 801–814. http://dx.doi.org/10.1016/0016-7037(91)90343-4.
Wang, J. and Buckley, J. S. 2003. Asphaltene Stability in Crude Oil and Aromatic Solvents—The Influence of Oil Composition. Energy Fuels 17 (6): 1445–1451. http://dx.doi.org/10.1021/ef030030y.
Wiehe, I. A. 2012. Asphaltene Solubility and Fluid Compatibility. Energy Fuels 26 (7): 4004–4016. http://dx.doi.org/10.1021/ef300276x.
Wiehe, I. A., Yarranton, H. W., Akbarzadeh, K. et al. 2005. The Paradox of Asphaltene Precipitation With Normal Paraffins. Energy Fuels 19 (4): 1261–1267. http://dx.doi.org/10.1021/ef0496956.
Yarranton, H. W., Alboudwarej, H., and Jakher, R. 2000. Investigation of Asphaltene Association With Vapor Pressure Osmometry and Interfacial Tension Measurements. Ind. Eng. Chem. Res. 39 (8): 2916–2924. http://dx.doi.org/10.1021/ie000073r.
Yen, T. F. and Chilingarian, G. V. 1994. Asphaltenes and Asphalts, first edition. New York City: Elsevier.
Zhao, B. and Shaw, J. M. 2007. Composition and Size Distribution of Coherent Nanostructures in Athabasca Bitumen and Maya Crude Oil. Energy Fuels 21 (5): 2795–2804. http://dx.doi.org/10.1021/ef070119u.