Phase Behavior and Adsorption of Pure Substances and Mixtures and Characterization in Nanopore Structures by Density Functional Theory
- Zhidong Li (Reservoir Engineering Research Institute) | Zhehui Jin (Reservoir Engineering Research Institute) | Abbas Firoozabadi (Yale University)
- Document ID
- Society of Petroleum Engineers
- SPE Journal
- Publication Date
- December 2014
- Document Type
- Journal Paper
- 1,096 - 1,109
- 2014.Society of Petroleum Engineers
- 5.2.2 Fluid Modeling, Equations of State, 5.2.1 Phase Behavior and PVT Measurements, 5.1 Reservoir Characterisation, 5.8.2 Shale Gas
- Nanopores, Shale gas
- 12 in the last 30 days
- 854 since 2007
- Show more detail
- View rights & permissions
|SPE Member Price:||USD 10.00|
|SPE Non-Member Price:||USD 30.00|
Phase behavior in shale remains a mystery because of various complexities and effects. One complexity is from nanopores, in which phase behavior is significantly affected by the interaction between the pore surfaces and fluid molecules. The result is a heterogeneous distribution of molecules that cannot be described by bulk phase thermodynamic approaches. Statistical thermodynamic methods can describe the phase behavior in nanopores. In this work, we apply an engineering density functional theory (DFT) combined with the Peng-Robinson equation of state (EOS) to investigate the adsorption and phase behavior of pure substances and mixtures in nanopores, and include the characterization of pore structure of porous media. The nanopores are represented by carbon-slit pores each consisting of two parallel planar-infinite structureless graphite surfaces. The porous medium are activated carbons and dry coal, each modeled by an array of polydisperse carbon-slit pores. We study the influence of multiple factors on phase transitions of various pure light species and their mixtures in nanopores. We find that capillary condensation and hysteresis are more likely in heavier hydrocarbons, at lower temperatures, and in smaller pores. For pure hydrocarbons in nanopores, the phase change always occurs below the critical temperature and saturation pressure. For mixtures in nanopores, there may be a phase change above the cricondentherm. We characterize the pore structure of porous media to obtain the pore-size distribution (PSD), surface area (SA), and pore volume (PV) on the basis of the measured adsorption isotherms of pure substances. Then, we use the computed PSD to predict the adsorption of mixtures in porous media. There is agreement between the experiments and our predictions. This work is in the direction of phase-behavior modeling and understanding in shale media.
|File Size||871 KB||Number of Pages||14|
Adesida, A. G., Akkutlu, I. Y., Resasco, D. E., et al. 2011. Characterization of Barnett Shale Kerogen Pore Size Distribution using DFT Analysis and Grand Canonical Monte Carlo Simulations. Presented at SPE Annual Technical Conference and Exhibition, Denver, Colorado, 30 October–2 November. SPE-147397-MS. http://dx.doi.org/10.2118/147397-MS.
Barret, E. P., Joyner, L. G., and Halenda, P. H. 1951. The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms. J. Am. Chem. Soc. 73 (1): 373–380. http://dx.doi.org/10.1021/ja01145a126.
Brunauer, S., Emmett, P.H., and Teller, E. 1938. Adsorption of Gases in Multimolecular Layers. J. Am. Chem. Soc. 60 (2): 309–319. http://dx.doi.org/10.1021/ja01269a023.
Chapman, W.G., Gubbins, K.E., Jackson, G., et al. 1989. SAFT: Equation-of-State Solution Model for Associating Fluids. Fluid Phase Equilibr. 52 (December): 31–38. http://dx.doi.org/10.1016/0378-3812(89)80308-5.
Chapman, W.G., Gubbins, K.E., Jackson, G., et al. 1990. New Reference Equation of State for Associating Liquids. Ind. Eng. Chem. Res. 29 (8): 1709–1721. http://dx.doi.org/10.1021/ie00104a021.
Chapman, W.G., Jackson, G., and Gubbins, K.E. 1988. Phase Equilibria of Associating Fluids. Chain Molecules with Multiple Bonding Sites. Mol. Phys. 65 (5): 1057–1079. http://dx.doi.org/10.1080/00268978800101601.
Cohan, L.H. 1938. Sorption Hysteresis and the Vapor Pressure of Concave Surfaces. J. Am. Chem. Soc. 60 (2): 433–435. http://dx.doi.org/10.1021/ja01269a058.
Dreibach, F., Staudt, R., and Keller, J. U. 1999. High Pressure Adsorption Data of Methane, Nitrogen, Carbon Dioxide and their Binary and Ternary Mixtures on Activated Carbon. Adsorption 5 (3): 215–227. http://dx.doi.org/10.1023/A:1008914703884.
Ebner, C. and Saam, W. F. 1977. New Phase-Transition Phenomena in Thin Argon Films. Phys. Rev. Lett. 38 (X): 1486–X. http://dx.doi.org/10.1103/PhysRevLett.38.1486.
Ebner, C., Saam, W. F., and Stroud, D. 1976. Density-Functional Theory of Simple Classical Fluids. I. Surfaces. Phys. Rev. A 14: 2264. http://dx.doi.org/10.1103/PhysRevA.14.2264.
Evans, R. 1996. Density Functionals in the Theory of Nonuniform Fuids. In Fundamentals of Inhomogeneous Fluids, ed. D. Henderson, Chap. 3, 85–176. New York City, New York: Marcel Dekker.
Firoozabadi, A. 1999. Thermodynamics of Hydrocarbon Reservoirs. New York City, New York: McGraw-Hill.
Gelb, L. D., Gubbins, K. E., Radhakrishnan, R., et al. 1999. Phase Separation in Confined Systems. Rep. Prog. Phys. 62 (12): 1573. http://dx.doi.org/10.1088/0034-4885/62/12/201.
Halsey, G. D. 1948. Physical Adsorption on Non-Uniform Surfaces. J. Chem. Phys. 16: 931–937. http://dx.doi.org/10.1063/1.1746689.
Jhaveri, B. S. and Youngren, G. K. 1988. Three-Parameter Modification of the Peng-Robinson Equation of State To Improve Volumetric Predictions. SPE Res Eval & Eng 3 (3): 1033–1040. SPE-13118-PA. http://dx.doi.org/10.2118/13118-PA.
Jiang, J. W. and Sandler, S. I. Adsorption and Phase Transitions on Nanoporous Carbonaceous Materials: Insights from Molecular Simulations. Fluid Phase Equilibr. 228–229 (February): 189–195. http://dx.doi.org/10.1016/j.fluid.2004.08.014.
Kuila, U. and Prasad, M. 2011. Understanding Pore-Structure And Permeability In Shales. Presented at SPE Annual Technical Conference and Exhibition, Denver, Colorado, 30 October–2 November. SPE-146869-MS. http://dx.doi.org/10.2118/146869-MS.
Langmuir, I. 1916. The Constitution and Fundamental Properties of Solids and Liquids. Part I. Solids. J. Am. Chem. Soc. 38 (11): 2221–2295. http://dx.doi.org/10.1021/ja02268a002.
Li, Z. and Firoozabadi, A. 2009. Interfacial Tension of Nonassociating Pure Substances and Binary Mixtures by Density Functional Theory Combined with Peng–Robinson Equation of State. J. Chem. Phys. 130 (15): 154108. http://dx.doi.org/10.1063/1.3100237.
Montgomery, S. L., Javie, D. M., Bowker, K. A., et al. 2005. Mississippian Barnett Shale, Fort Worth Basin, North-Central Texas: Gas-Shale Play with Multi–Trillion Cubic Foot Potential. AAPG Bull. 89 (2): 155–175. http://dx.doi.org/10.1306/09170404042.
Monsalvo, M. and Shapiro, A. 2007. Modeling Adsorption of Binary and Ternary Mixtures on Microporous Media. Fluid Phase Equilibr. 254 (1–2): 91–100. http://dx.doi.org/10.1016/j.fluid.2007.02.006.
Monsalvo, M. and Shapiro, A. 2009a. Modeling Adsorption of Liquid Mixtures on Porous Materials. J. Colloid Interf. Sci. 333 (1): 310–316. http://dx.doi.org/10.1016/j.jcis.2009.01.055.
Monsalvo, M. and Shapiro, A. 2009b. Study of High-Pressure Adsorption from Supercritical Fluids by the Potential Theory. Fluid Phase Equilibr. 283 (1–2): 56–64. http://dx.doi.org/10.1016/j.fluid.2009.05.015.
Myers, A. L. and Prausnitz, J. M. 1965. Thermodynamics of Mixed-Gas Adsorption. AIChE J. 11 (1): 121–127. http://dx.doi.org/10.1002/aic.690110125.
Olivier, J.P. 1995. Modeling Physical Adsorption on Porous and Nonporous Solids Using Density Functional Theory. J. Porous Mat. 2 (1): 9–17. http://dx.doi.org/10.1007/BF00486565.
Ottiger, S., Pini, R., Storti, G., et al. 2008a. Competitive Adsorption Equilibria of CO2 and CH4 on a Dry Coal. Adsorption 14 (4–5): 539–556. http://dx.doi.org/10.1007/s10450-008-9114-0.
Ottiger, S., Pini, R., Storti, G., et al. 2008b. Measuring and Modeling the Competitive Adsorption of CO2, CH4, and N2 on a Dry Coal. Langmuir 24 (17): 9531–9540. http://dx.doi.org/10.1021/la801350h.
Peng, D.Y. and Robinson, D. B. 1976. A New Two-Constant Equation of State. Ind. Eng. Chem. Fundamen. 15 (1): 59–64. http://dx.doi.org/10.1021/i160057a011.
Qiao, S. Z., Wang, K., and Hu, X. J. 2000. Using Local IAST with Micropore Size Distribution To Predict Multicomponent Adsorption Equilibrium of Gases in Activated Carbon. Langmuir 16 (3): 1292–1298. http://dx.doi.org/10.1021/la990785q.
Rangarajan, B., Lira, C.T., and Subramanian, R. 1995. Simplified Local Density Model for Adsorption Over Large Pressure Ranges. AIChE J. 41 (4): 838–845. http://dx.doi.org/10.1002/aic.690410411.
Ravikovitch, P. I., Vishnyakov, A., Russo, R., et al. 2000. Unified Approach to Pore Size Characterization of Microporous Carbonaceous Materials from N2, Ar, and CO2 Adsorption Isotherms. Langmuir 16 (5): 2311–2320. http://dx.doi.org/10.1021/la991011c.
Robinson, D. B., Peng, D. Y., and Chung, S. Y. K. 1985. The Development of the Peng-Robinson Equation and its Application to Phase Equilibrium in a System Containing Methanol. Fluid Phase Equilibr. 24 (1–2): 25–41. http://dx.doi.org/10.1016/0378-3812(85)87035-7.
Roque-Malherbe, R. M. A. 2007. Adsorption and Diffusion in Nanoporous Materials. Boca Raton, Florida: CRC Press.
Rosenfeld, Y. 1989. Free-Energy Model for the Inhomogeneous Hard-Sphere Fluid Mixture and Density-Functional Theory of Freezing. Phys. Rev. Lett. 63 (9): 980–983. http://dx.doi.org/10.1103/PhysRevLett.63.980.
Shapiro, A. and Stenby, E. 1998. Analysis of Multicomponent Adsorption Close to a Dew Point. J. Colloid Interf. Sci. 206 (2): 546–557. http://dx.doi.org/10.1006/jcis.1998.5683.
Singh, S. K., Sinha, A., Deo, G., et al. 2009. Vapor−Liquid Phase Coexistence, Critical Properties, and Surface Tension of Confined Alkanes. J. Phys. Chem. C 113 (17): 7170–7180. http://dx.doi.org/10.1021/jp8073915.
Steele, W. A. 1973. The Physical Interaction of Gases with Crystalline Solids: I. Gas-Solid Energies and Properties of Isolated Adsorbed Atoms. Surf. Sci. 36 (1): 317–352. http://dx.doi.org/10.1016/0039-6028(73)90264-1.
Subramanian, R., Pyada, H., and Lira, C. T. 1995. An Engineering Model for Adsorption of Gases onto Flat Surfaces and Clustering in Supercritical Fluids. Ind. Eng. Chem. Res. 34 (11): 3830–3837. http://dx.doi.org/10.1021/ie00038a021.
Sudibandriyo, M., Pan, Z. J., Fitzgerald, J. E., et al. 2003. Adsorption of Methane, Nitrogen, Carbon Dioxide, and Their Binary Mixtures on Dry Activated Carbon at 318.2 K and Pressures up to 13.6 Mpa. Langmuir 19 (13): 5323–5331. http://dx.doi.org/10.1021/la020976k.
Sweatman, M. B. and Quirke, N. 2001. Characterization of Porous Materials by Gas Adsorption at Ambient Temperatures and High Pressure. J. Phys. Chem. B 105 (7): 1403–1411. http://dx.doi.org/10.1021/jp003308l.
Sweatman, M. B. and Quirke, N. 2002. Predicting the Adsorption of Gas Mixtures: Adsorbed Solution Theory versus Classical Density Functional Theory. Langmuir 18 (26): 10443–10454. http://dx.doi.org/10.1021/la0200358.
Ustinov, E. A., and Do, D. D. 2003. High-Pressure Adsorption of Supercritical Gases on Activated Carbons: An Improved Approach Based on the Density Functional Theory and the Bender Equation of State. Langmuir 19 (20): 8349–8357. http://dx.doi.org/10.1021/la030119w.
Wu, J. 2006. Density Functional Theory for Chemical Engineering: From Capillarity to Soft Materials. AIChE J. 52 (3): 1169–1193. http://dx.doi.org/10.1002/aic.10713.
Wu, J. 2009. Density Functional Theory for Liquid Structure and Thermodynamics. In Molecular Thermodynamics of Complex Systems, ed. X. H. Lu and Y. Hu, New York: Springer.
Wu, J. and Li, Z. 2007. Density-Functional Theory for Complex Fluids. Annu. Rev. Phys. Chem. 58: 85–112. http://dx.doi.org/10.1146/annurev.physchem.58.032806.104650.