Volume-translated cubic EoS and PC-SAFT density models and a free volume-based viscosity model for hydrocarbons at extreme temperature and pressure conditions

Abstract This research focuses on providing the petroleum reservoir engineering community with robust models of hydrocarbon density and viscosity at the extreme temperature and pressure conditions (up to 533 K and 276 MPa, respectively) characteristic of ultra-deep reservoirs, such as those associated with the deepwater wells in the Gulf of Mexico. Our strategy is to base the volume-translated (VT) Peng–Robinson (PR) and Soave–Redlich–Kwong (SRK) cubic equations of state (EoSs) and perturbed-chain, statistical associating fluid theory (PC-SAFT) on an extensive data base of high temperature (278–533 K), high pressure (6.9–276 MPa) density rather than fitting the models to low pressure saturated liquid density data. This high-temperature, high-pressure (HTHP) data base consists of literature data for hydrocarbons ranging from methane to C40. The three new models developed in this work, HTHP VT-PR EoS, HTHP VT-SRK EoS, and hybrid PC-SAFT, yield mean absolute percent deviation values (MAPD) for HTHP hydrocarbon density of ∼2.0%, ∼1.5%, and An effort was also made to provide accurate hydrocarbon viscosity models based on literature data. Viscosity values are estimated with the frictional theory (f-theory) and free volume (FV) theory of viscosity. The best results were obtained when the PC-SAFT equation was used to obtain both the attractive and repulsive pressure inputs to f-theory, and the density input to FV theory. Both viscosity models provide accurate results at pressures to 100 MPa but experimental and model results can deviate by more than 25% at pressures above 200 MPa.

[1]  Mark A. McHugh,et al.  Equation of state modeling of high-pressure, high-temperature hydrocarbon density data , 2010 .

[2]  IIya Polishuk Generalization of SAFT + Cubic equation of state for predicting and correlating thermodynamic properties of heavy organic substances , 2012 .

[3]  Jürgen Gmehling,et al.  Improvement of the SRK equation of state for representing volumetric properties of petroleum fluids using Dortmund Data Bank , 1999 .

[4]  M. Satyro,et al.  Expanded Fluid-Based Viscosity Correlation for Hydrocarbons , 2009 .

[5]  Stanley H. Huang,et al.  Equation of state for small, large, polydisperse, and associating molecules , 1990 .

[6]  I. Polishuk Modeling of Viscosities in Extended Pressure Range Using SAFT + Cubic EoS and Modified Yarranton–Satyro Correlation , 2012 .

[7]  D. Lempe,et al.  Density improvement of the SRK equation of state , 1997 .

[8]  D. Peng,et al.  A New Two-Constant Equation of State , 1976 .

[9]  M. Satyro,et al.  Viscosity prediction for natural gas processing applications , 2012 .

[10]  J. García,et al.  General friction theory viscosity model for the PC‐SAFT equation of state , 2006 .

[11]  M. Modell,et al.  Density-and-temperature-dependent volume translation for the SRK EOS: 1. Pure fluids , 2009 .

[12]  Arthur K. Doolittle,et al.  Specific Volumes of n-Alkanes. , 1964 .

[13]  G. Soave Equilibrium constants from a modified Redlich-Kwong equation of state , 1972 .

[14]  Deepak Tapriyal,et al.  Prediction of fluid density at extreme conditions using the perturbed-chain SAFT equation correlated to high temperature, high pressure density data , 2012 .

[15]  Stanley H. Huang,et al.  Equation of state for small, large, polydisperse, and associating molecules: extension to fluid mixtures , 1991 .

[16]  Erling Halfdan Stenby,et al.  The friction theory (f-theory) for viscosity modeling , 2000 .

[17]  Ho-mu Lin,et al.  Gas-liquid equilibrium in binary mixtures of methane with N-decane, benzene, and toluene , 1979 .

[18]  A. Allal,et al.  Free-volume viscosity model for fluids in the dense and gaseous states. , 2001, Physical review. E, Statistical, nonlinear, and soft matter physics.

[19]  Andre Peneloux,et al.  A consistent correction for Redlich-Kwong-Soave volumes , 1982 .

[20]  Gabriele Sadowski,et al.  Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for Chain Molecules , 2001 .

[21]  George Jackson,et al.  New reference equation of state for associating liquids , 1990 .

[22]  George Jackson,et al.  Phase equilibria of associating fluids , 2006 .

[23]  J. D. Isdale,et al.  Transport properties of nonelectrolyte liquid mixtures—VII. Viscosity coefficients for isooctane and for equimolar mixtures of isooctane + n-octane and isooctane + n-dodecane from 25 to 100°C at pressures up to 500 MPa or to the freezing pressure , 1985 .

[24]  K. E. Starling,et al.  Generalized multiparameter correlation for nonpolar and polar fluid transport properties , 1988 .

[25]  M. Satyro,et al.  Predicting the Viscosity of Asymmetric Hydrocarbon Mixtures with the Expanded Fluid Viscosity Correlation , 2011 .

[26]  Arthur K. Doolittle,et al.  Studies in Newtonian Flow. II. The Dependence of the Viscosity of Liquids on Free‐Space , 1951 .

[27]  Deepak Tapriyal,et al.  Prediction of hydrocarbon densities at extreme conditions using volume-translated SRK and PR equations of state fit to high temperature, high pressure PVT data , 2012 .

[28]  E. Stenby,et al.  One parameter friction theory models for viscosity , 2001 .

[29]  I. Polishuk Till which pressures the fluid phase EOS models might stay reliable , 2011 .

[30]  Kun Liu,et al.  Experimental measurements and equation of state modeling of liquid densities for long-chain n-alkanes at pressures to 265 MPa and temperatures to 523 K , 2011 .

[31]  W. Wakeham,et al.  The Viscosity and Density of n-Dodecane and n-Octadecane at Pressures up to 200 MPa and Temperatures up to 473 K , 2004 .

[32]  I. Polishuk Hybridizing SAFT and Cubic EOS: What Can Be Achieved? , 2011 .