A Comparison of Mixing Rules for the Combination of COSMO-RS with the Peng-Robinson Equation of State

Abstract In this work, the COSMO-RS model is combined with a volume-translated Peng–Robinson equation of state (EOS) via a G E -based mixing rule. The performance of several mixing rules previously published for this purpose is compared and semi-empirical modifications to one of them are introduced to improve its performance in our application. The new mixing rule contains three internal parameters that are adjusted to achieve consistency between the mixing rule and COSMO-RS. No experimental binary data is needed for our EOS. The new COSMO-RS-based, predictive EOS introduces a density dependence into COSMO-RS and extends its applicability to higher pressures and to mixtures containing supercritical components.

[1]  Ming-Tsung Lee,et al.  Prediction of mixture vapor–liquid equilibrium from the combined use of Peng–Robinson equation of state and COSMO-SAC activity coefficient model through the Wong–Sandler mixing rule , 2007 .

[2]  S. Sandler,et al.  Equation of state mixing rule for nonideal mixtures using available activity coefficient model parameters and that allows extrapolation over large ranges of temperature and pressure , 1992 .

[3]  Joseph J. Martin.  Cubic Equations of State-Which? , 1979 .

[4]  Roland Span,et al.  Multiparameter Equations of State: An Accurate Source of Thermodynamic Property Data , 2000 .

[5]  Ulrich K. Deiters,et al.  A Modular Program System for the Calculation of Thermodynamic Properties of Fluids , 2000 .

[6]  Y. Shimoyama,et al.  Prediction of phase equilibria for mixtures containing water, hydrocarbons and alcohols at high temperatures and pressures by cubic equation of state with GE type mixing rule based on COSMO-RS , 2006 .

[7]  H. Baehr,et al.  An International Standard Formulation for the Thermodynamic Properties of 1,1,1,2‐Tetrafluoroethane (HFC‐134a) for Temperatures from 170 K to 455 K and Pressures up to 70 MPa , 1994 .

[8]  A. Klamt,et al.  Vapor–liquid equilibrium prediction at high pressures using activity coefficients at infinite dilution from COSMO-type methods , 2005 .

[9]  A. Peneloux,et al.  Group-contribution equation of state for correlating and predicting thermodynamic properties of weakly polar and non-associating mixtures: Binary and multicomponent systems , 1991 .

[10]  A. Klamt,et al.  COSMO : a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient , 1993 .

[11]  Chiehming J. Chang,et al.  Densities and P-x-y diagrams for carbon dioxide dissolution in methanol, ethanol, and acetone mixtures , 1997 .

[12]  W. Wagner,et al.  A New Equation of State for Carbon Dioxide Covering the Fluid Region from the Triple‐Point Temperature to 1100 K at Pressures up to 800 MPa , 1996 .

[13]  S. Saito,et al.  Measurement of vapor-liquid equilibria at elevated temperatures and pressures using a flow type apparatus. , 1986 .

[14]  Socrates Ioannidis,et al.  Vapor–liquid equilibria predictions at high-pressures with the Huron–Vidal mixing rule , 2001 .

[15]  L. Vecchiato,et al.  Equation-of-State Group Contributions from Infinite-Dilution Activity Coefficients , 1994 .

[16]  S. Sandler,et al.  A comparison of Huron-Vidal type mixing rules of mixtures of compounds with large size differences, and a new mixing rule , 1997 .

[17]  Jürgen Gmehling,et al.  Development of an universal group contribution equation of state , 2001 .

[18]  Y. Ma,et al.  Multiphase and Volumetric Equilibria of the Ethane-Methanol System at Temperatures between -40 C. and 100 C. , 1964 .

[19]  John J. Carroll,et al.  The equilibrium phase properties of the methanol-hydrogen sulfide binary system , 1992 .

[20]  Aage Fredenslund,et al.  A modified UNIFAC group-contribution model for prediction of phase equilibria and heats of mixing , 1987 .

[21]  N. Xu,et al.  Vapor-liquid equilibria of five binary systems containing R-22 , 1991 .

[22]  Jürgen Gmehling,et al.  Development of a Universal Group Contribution Equation of State. 2. Prediction of Vapor-Liquid Equilibria for Asymmetric Systems , 2002 .

[23]  Aage Fredenslund,et al.  Group‐contribution estimation of activity coefficients in nonideal liquid mixtures , 1975 .

[24]  Daniel G. Friend,et al.  Thermophysical Properties of Ethane , 1991 .

[25]  K. Lucas,et al.  Experimental vapor-liquid equilibria in the systems R 22-R 23, R 22-Co2, Cs2-R 22, R 23-Co2, Cs2-R 23 and their correlation by equations of state , 1992 .

[26]  H. Masuoka,et al.  Solubility of carbon dioxide in eicosane, docosane, tetracosane, and octacosane at temperatures from 323 to 473 K and pressures up to 40 MPa , 1998 .

[27]  M. Hirata,et al.  BINARY VAPOR-LIQUID EQUILIBRIA OF CARBON DIOXIDE-LIGHT HYDROCARBONS AT LOW TEMPERATURE , 1974 .

[28]  K. Leonhard,et al.  Making Equation of State Models Predictive−Part 3: Improved Treatment of Multipolar Interactions in a PC-SAFT Based Equation of State† , 2007 .

[29]  S. G. Penoncello,et al.  A Fundamental Equation for Trifluoromethane (R-23) , 2003 .

[30]  G. Thodos,et al.  Vapor—liquid equilibrium measurements for the methanol—acetone system at 372.8, 397.7 and 422.6 K , 1986 .

[31]  E. Voutsas,et al.  Thermodynamic property calculations with the universal mixing rule for EoS/GE models: Results with the Peng–Robinson EoS and a UNIFAC model , 2006 .

[32]  G. Thodos,et al.  Vapor‐liquid equilibrium measurements for the propane‐ethanol system at elevated pressures , 1978 .

[33]  Jürgen Gmehling,et al.  Performance of a Conductor-Like Screening Model for Real Solvents Model in Comparison to Classical Group Contribution Methods , 2005 .

[34]  Michael L. Michelsen,et al.  A modified Huron-Vidal mixing rule for cubic equations of state , 1990 .

[35]  A. Klamt,et al.  COSMO-RS: a novel and efficient method for the a priori prediction of thermophysical data of liquids , 2000 .

[36]  J. E. Coon,et al.  Connection between zero-pressure mixing rules and infinite-pressure mixing rules , 1998 .

[37]  D. Tassios,et al.  Capabilities and limitations of the Wong-Sandler mixing rules , 1995 .

[38]  M. Huron,et al.  New mixing rules in simple equations of state for representing vapour-liquid equilibria of strongly non-ideal mixtures☆ , 1979 .

[39]  Wolfgang Wagner,et al.  A New Equation of State and Tables of Thermodynamic Properties for Methane Covering the Range from the Melting Line to 625 K at Pressures up to 100 MPa , 1991 .

[40]  J. Zollweg,et al.  Vapor-liquid equilibrium in the system carbon dioxide + 2,2-dimethylpropane from 262 to 424 K at pressures to 8.4 MPa , 1990 .

[41]  P. Marteau,et al.  Experimental determination of the phase behavior of binary mixtures: methanehexane and methanebenzene , 1997 .

[42]  J. Gmehling.  Vapor-Liquid Equilibrium Data Collection , 1977 .

[43]  David Shan-Hill Wong,et al.  A theoretically correct mixing rule for cubic equations of state , 1992 .

[44]  F. Barr-David,et al.  Vapor-Liquid Equilibrium at High Pressures. The Systems Ethanol-Water and 2-Propanol-Water. , 1959 .

[45]  A. Klamt.  Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena , 1995 .

[46]  Dimitrios P. Tassios,et al.  Universal Mixing Rule for Cubic Equations of State Applicable to Symmetric and Asymmetric Systems: Results with the Peng−Robinson Equation of State , 2004 .

[47]  H. Miyamoto,et al.  A Thermodynamic Property Model for Fluid-Phase Propane , 2000 .

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

[49]  R. Reid,et al.  The Properties of Gases and Liquids , 1977 .

[50]  J. Gmehling,et al.  Performance of COSMO-RS with Sigma Profiles from Different Model Chemistries , 2007 .

[51]  Joosup. Shim,et al.  Multiphase and Volumetric Equilibria of Methane-n-Hexane Binary System at Temperatures Between -110° and 150° C. , 1962 .

[52]  A. Fredenslund,et al.  Measurement and prediction of equilibrium ratios for the C2H6+ CO2 system , 1974 .

[53]  S. Beyerlein,et al.  Application of nonlinear regression in the development of a wide range formulation for HCFC-22 , 1995 .

[54]  K. Tochigi.  Prediction of high-pressure vapor-liquid equilibria using ASOG , 1995 .

[55]  Stanley H. Huang,et al.  Solubility of carbon dioxide, methane, and ethane in n-eicosane , 1988 .

[56]  R. Heidemann.  Excess free energy mixing rules for cubic equations of state , 1996 .

[57]  S. Sandler,et al.  Prediction of vapor-liquid equilibria at high pressures using activity coefficient parameters obtained from low-pressure data : a comparison of two equation of state mixing rules , 1993 .

[58]  Vargaftik,et al.  Handbook of Physical Properties of Liquids and Gases , 1983 .

[59]  D. Richon,et al.  Vapor-liquid equilibrium data for the propane-methanol and propane-methanol-carbon dioxide system , 1986 .

[60]  J. Gmehling,et al.  PSRK: A Group Contribution Equation of State Based on UNIFAC , 1991 .

[61]  Stanley I. Sandler,et al.  A Priori Phase Equilibrium Prediction from a Segment Contribution Solvation Model , 2002 .

[62]  Chorng H. Twu,et al.  A new generalized alpha function for a cubic equation of state Part 1. Peng-Robinson equation , 1995 .

[63]  J. Gmehling,et al.  A modified UNIFAC model. 1. Prediction of VLE, hE, and .gamma..infin. , 1987 .

[64]  W. Wagner,et al.  The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use , 2002 .

[65]  M. Medani,et al.  Thermodynamic properties of methanol–benzene mixtures at elevated temperatures , 2007 .

[66]  Stanley I. Sandler,et al.  On the combination of equation of state and excess free energy models , 1995 .

[67]  K. Tochigi.  Prediction of Vapor-Liquid Equilibria in Non-Polymer and Polymer Solutions Using an ASOG-Based Equation of State(PRASOG) , 1998 .

[68]  Ming-Jer Lee,et al.  Vapor-liquid equilibrium of the octane/carbon dioxide, octane/ethane, and octane/ethylene systems , 1992 .