Document Type : Research Paper


Assistant Professor, Chemical and Petroleum Engineering Department, Ilam University, P.O. Box 69315/516, Ilam, Iran


Using nanoparticles for adsorbing asphaltene is an efficient method for upgrading actual oil samples compared to other expensive mechanical treatments or even solvents, such as n-pentane and n-heptane, and surfactants. This study uses nickel–zeolite oxide nanoparticles for asphaltene adsorption and solving asphaltene precipitation problems. Although nickel–zeolite oxide nanoparticles have been used in previous studies as an asphaltene adsorbent, observing the relationship between asphaltene adsorption on their surface and asphaltene precipitation in the presence of nanoparticles during the actual process is not covered. For addressing this relation, we performed a series of experiments included Fourier-transform infrared spectroscopy (FTIR), CO2–oil interfacial tension tests, Langmuir and Freundlich isotherm models, and natural depletion tests in the presence of nickel–zeolite oxide nanoparticles. The Langmuir model better fitted the adsorption data than the Freundlich model, which shows that the adsorption occurs on a homogeneous surface with monolayer coverage. Based on the CO2–oil interfacial tension results, there are two different slope forms in interfacial tension readings as pressure increases from 150 to 1650 psi. Due to asphaltene aggregation, the second slope (900–1650 psi) is slower than the first one (150–900 psi). Three pressures of 1350, 1500, and 1650 psi and nickel–zeolite oxide nanoparticles at a concentration of 30 ppm were selected for the natural depletion tests, and the basis of selection was high-efficiency adsorption at these points. As pressure decreased from 1650 to 1350 psi, asphaltene precipitation changed from 8.25 to 10.52 wt % in the base case, and it varied from 5.17 to 7.54 wt % in the presence of nickel–zeolite oxide at a concentration of 30 ppm. Accordingly, nickel–zeolite oxide nanoparticles adsorbed asphaltene on their surface correctly, and the amount of asphaltene precipitation decreased in the presence of nickel–zeolite oxide nanoparticles.


Main Subjects

Ahmadi, Y., Aminshahidy, Y. Effects of hydrophobic CaO and SiO2 nanoparticles on Asphaltene Precipitation Envelope APE: an experimental and modeling approach, Oil & Gas Science and Technology–Revue d’IFP Energies Nouvelles, Vol. 73, No. 46, pp. 11, 2018.
Ahmadi, Y., Aminshahidy, Y. Inhibition of asphaltene precipitation by hydrophobic CaO and SiO2 nanoparticles during natural depletion and CO2 tests, Int. J. Oil, Gas and Coal Technology, Vol. 24, No. 3, pp. 394–414, 2020.
Alboudwarej, H., Pole, D., Svrcek, W. Y. and Yarranton, H. W. Adsorption of asphaltenes on metals. Ind. Eng. Chem. Res., Vol. 44, No. 15, pp. 5585–5592, 2005.
ASTM D6560-17, Standard Test Method for Determination of Asphaltenes Heptane Insoluble in Crude Petroleum and Petroleum Products, ASTM International, West Conshohocken, PA, 2017.
Balabin, R. M., Syunyaev, R. Z., Schmid, T., Stadler, J., Lomakina, E. I. and Zenobi, R. Asphaltene Adsorption onto an Iron Surface: Combined Near-Infrared NIR, Raman, and AFM Study of the Kinetics, Thermodynamics, and Layer Structure. Energy Fuels, Vol. 25, pp. 189–196, 2011.
Bantignies, J.-L., Cartier dit Moulin, C. and Dexpert, H. Asphaltene adsorption on kaolinite characterized by infrared and X-ray absorption spectroscopies. J. Pet. Sci. Eng. Vol. 20 No. 4, pp. 233–237, 1988.
Derrick, M. R., Stulik, D., and Landry, J. M. Infrared Spectroscopy in Conservation Science, The Getty Conservation Institute, 1999.
Fakeeha, A. H., Al-Fatesh, A. S., Abasaeed, A. E., Stabilities of zeolite-supported Ni catalysts for dry reforming of methane. Chin. J. Catal, Vol. 34, pp. 764–768, 2013.
Field, L. D., Sternhell, S., and Kalman, J. R. 2008 ̒Organic Structures from Spectra, 4th Ed, John Wiley & Sons Ltd., Chichester, 2008.
Franco, C. A., Montoya, T., Nassar, N. N., Pereira-Almao, P. and Cortes, F. B., Adsorption and Subsequent Oxidation of Colombian Asphaltenes onto Nickel and Palladium Oxide Supported on Fumed Silica Nanoparticles, Energy Fuels, Vol. 27, No. 12, pp. 7336–7347, 2013. DOI: 10.1021/ef4000825.
Franco, C., Patiño, E., Benjumea, P., Ruiz, M. A. and Cortés, F. B. 2013 Kinetic and thermodynamic equilibrium of asphaltenes sorption onto nanoparticles of nickel oxide supported on nanoparticulated alumina. Fuel, Vol. 105, pp. 408–414.
Gonzalez, M. F., Sosa-Stull, C., Lopez-Linares, F. and Pereira-Almao, P, Comparing asphaltene adsorption with model heavy molecules over macroporous solid surfaces̕ Energy Fuels, Vol. 21, pp. 234–241, 2007.
Hashemi, R., Nassar, N. N., and Pereira-Almao, P. R. In situ Upgrading of Athabasca Bitumen Using Multimetallic Ultra-Dispersed Nanocatalysts in an Oil-Sands-Packed Bed Column: Part 1, Produced Liquid Quality Enhancement, Energy & Fuels, Vol. 28, No. 2, pp. 1338–1350, 2013.
Hashemi, R., Nassar, N. N., and Pereira-Almao, P. Transport behavior of multi metallic ultra-dispersed nanoparticles in an oil-sands-packed bed column at a high temperature and pressure, Energy Fuels, Vol. 26, No. 3, pp. 1645–1655, 2013. DOI: 10.1021/ef201939f.
He, Y., Zeolite supported Fe/Ni bimetallic nanoparticles for simultaneous removal of nitrate and phosphate: synergistic effect and mechanism. Chemical Engineering Journal, Vol. 347, pp. 669–681, 2018.
Hemmati-Sarapardeh, A., Alipour-Yeganeh-Marand, R., Naseri, A., Safiabadi, A., Gharagheizi, F., IlaniKashkouli, pp. and Mohammadi, A.H., Asphaltene precipitation duet natural depletion of reservoir: Determination using a SARA fraction based intelligent model. Fluid Phase equilibria, Vol. 354, pp. 177–184, 2013. DOI:10.1016/j.fluid.2013.06.005.
Hosseinpour, N., Asphaltene adsorption onto acidic/basic metal oxide nanoparticles toward in situ upgrading of reservoir oils by nanotechnology. Langmuir, Vol. 29, pp. 14135–14146, 2013.
Hosseinpour, N., Mortazavi, Y., Bahramian, A., Khodatars, L., Khodadadi. A.A., Enhanced Pyrolysis and Oxidation of Asphaltenes Adsorbed onto Transition Metal Oxides Nanoparticles towards Advanced in-Situ Combustion. EOR Processes by Nanotechnology. Applied Catalysis A: General, Vol. 477, p. 159–171, 2014.
Karimi, A., Fakhroueian, Z., Bahramian, A., Khiabani, N. P., Darabad, J. B., Azin, R. and Arya S. Wettability alteration in Carbonates using Zirconium Oxide Nanofluids: EOR Implications, Energy Fuels, Vol. 26, No. 2, pp. 1028–1036, 2012. DOI: 10.1021/ef201475u.
Kashefi, S., Lotfollahi, M. N. and Shahrabadi, A. Investigation of Asphaltene Adsorption onto Zeolite Beta Nanoparticles to Reduce Asphaltene Deposition in a Silica Sand Pack, Oil & Gas Science and Technology Rev. IFP Energies Nouvelles, Vol. 73, No. 2, 2018.
Kashefi, S., Lotfollahia, M. N., and Shahrabadib, A., Asphaltene Adsorption using Nanoparticles with Different Surface Chemistry: Equilibrium and Thermodynamics Studies. Petroleum Chemistry, 59, pp. 1201–1206, 2019.
Kazemzadeh, Y.; Eshraghi, S.E.; Kazemi, K.; Sourani, S.; Mehrabi, M.; Ahmadi, Y., Behavior of asphaltene adsorption onto the metal oxide nanoparticle surface and its effect on heavy oil recovery. Ind. Eng. Chem. Res, Vol. 54, pp. 233–239, 2015.
Kosinov, N., Liu, C., Hensen, E. J., Pidko, E. A., Engineering of transition metal catalysts confined in zeolites. Chem. Mate, Vol. 30, pp. 3177–3198, 2018.
Kralova, I., Sjöblom, J., Øye, G., Simon, S., Grimes, B. A. and Paso, K., Heavy crude oils/particle stabilized emulsions, Adv. Colloid Interface Sci, Vol. 169, No. 2, pp. 106–127, 2011. DOI:10.1016/j.cis.2011.09.001.
Lei, J., Niu, R., Li, J., and Wang, S., The Pd/Na-ZSM-5 catalysts with different Si/Al ratios on low concentration methane oxidation. Solid-State Sciences, Vol. 101, pp. 1060–97, 2020.
Li, X., Effect of nanoparticles on asphaltene aggregation in a microsized pore. Ind Eng Chem Res. Vol. 57, pp. 9009–9017, 2018.
Lopez-Linares, F., Carbognani-Arambarri, L., Gonzalez, M. F., Sosa-Stull, C., Figueras, M. and Pereira-Almao, P. Quinolin-65 and violanthrone-79 as model molecules for the kinetics of the adsorption of C7 Athabasca asphaltene on macroporous solid surfaces̒, Energy Fuels, Vol. 20, pp. 2748–2750, 2006.
Mansouri, M., Parhiz, M., Bayati, B., Ahmadi, Y. Preparation of Nickel Oxide Supported Zeolite catalyst NiO/Na-ZSm-5 for Asphaltene Adsorption: A Kinetic and Thermodynamic Study, Vol. 10, NO. 2, pp. 24, 2021.
Mayo, D. W., Miller, F. A., and Hannah, R. W. Course notes on the interpretation of infrared and Raman spectra. John Wiley & Sons, Inc., 2003.
Naghdi, N. and Mirzayi, B. Adsorption and Removal of Asphaltene Using Synthesized Maghemite and Hematite Nanoparticles, Energy Fuels, Vol. 29, No. 3, pp. 1397–1406, 2015. DOI: 10.1021/ef502494d.
Nassar N. N., Hassan A., and Pereira Almao P., Thermogravimetric studies on the catalytic effect of metal oxide nanoparticles on asphaltene pyrolysis under inert conditions. Thermal Analysis and Calorimetry, Vol. 110, p. 1327–1332, 2011.
Nassar, N. N. 2010., Asphaltene adsorption onto alumina nanoparticles: kinetics and thermodynamic studies. Energy Fuels, Vol. 24, No. 8, pp. 4116–4122.
Nassar, N. N., Hassan, A., and Pereira-Almao, P., Effect of surface acidity and basicity of aluminas on asphaltene adsorption and oxidation. J. Colloid Interface Sci., Vol. 360, No. 1, pp. 233–238, 2011.
Nassar, N. N., Hassan, A. Pereira-Almao, P., Metal oxide nanoparticles for asphaltene adsorption and oxidation. Energy Fuels, Vol. 25 No. 3, pp. 1017–1023, 2011.
Olvera, J. N. R., Gutierrez, G. J., Serrano, J. Ovando, A. M., Febles, V. G. and Arceo, L. D. B. Use of unsupported, mechanically alloyed NiWMoC nanocatalyst to reduce the viscosity of aqua thermolysis reaction of heavy oil, Catalysis Communications, Vol. 43 pp. 131–135, 2014.
Östlund, J. A., Wattana, P., Nydén, M. and Fogler, H. S., Characterization of fractionated asphaltenes by UV–vis and NMR self-diffusion spectroscopy. J. Colloid Interface Sci, Vol. 271, No. 2, pp. 372–380, 2004. DOI: 10.1016/j.jcis.2003.10.033.
Pernyeszi, T. and Dékány, I. Sorption and elution of asphaltenes from porous silica surfaces, Colloids Surf, A, Vol. 194 No. 3, pp. 25–39, 2001.
Pernyeszi, T., Patzkó, Á., Berkesi, O. and Dékány, I. Asphaltene adsorption on clays and crude oil reservoir rocks. Colloids Surf., A, Vol. 137, No. 3, pp. 373–384, 1988.
Rudyk, S. and Spirov, P., Upgrading and extraction of bitumen from Nigerian tar sand by supercritical carbon dioxide. API Energy, Vol. 113, pp. 1397–1404, 2014. DOI: 10.1016/j.apenergy.2013.08.076.
Sedighi, M., Mohammadi, M., Application of Green Novel NiO/ZSM-5 for Removal of Lead and Mercury ions from Aqueous Solution: Investigation of Adsorption Parameters. J. Water Environ. Nanotechnol, Vol. 34, pp. 301–310, 2018.
Silverstein, R. M., Webster, F. X., and Kiemle, D. J.Spectrometric identification of organic compounds, 7th ed, John Wiley & Sons, Ltd, New York, 2005.
Stuart, B. Infrared spectroscopy: fundamentals and applications, John Wiley & Sons Ltd., Chichester.
Thawer, R., Nicoll, D. C. A. and Dick, G., Asphaltene deposition in production facility, SPE Prod. Eng, Vol. 5, pp. 475–480, 2004. DOI: 10.2118/18473-PA.
Trbovich, M. G. and King, G. E. Asphaltene Deposit Removal: Long-Lasting Treatment with a Co-Solvent, Paper SPE-21038-MS Presented at the SPE International Symposium on Oilfield Chemistry, 20–22 February 1991. Anaheim, California, USA. DOI: 10.2118/21038-MS.
Valter Antonio, M. B., Mansoori, G. A., De Almeida Xavier, L. C.; Park, S. J., and Manafi, H. Asphaltene flocculation and collapse from petroleum fluids. J. Pet. Sci. Eng, Vol. 32, pp. 217–230, 2001 DOI: 10.1016/S0920-41050100163-2.
Yarranton, H. W., Alboudwarej, H. and Jakher, R. Investigation of Asphaltene Association with Vapor Pressure Osmometry and Interfacial Tension Measurements. Ind. Eng. Chem. Res., Vol. 39, No. 8, pp. 2916–2924, 2000. DOI: 10.1021/ie000073r.