Evaluation of the CO2 Behavior in Binary Mixtures with Alkanes, Alcohols, Acids and Esters Using the Cubic-Plus-Association Equation of State

Abstract Knowledge regarding the high pressure phase behavior of CO 2 mixtures is of primary importance for designing, operating and optimizing many industrial processes, such as supercritical fluid extraction for pharmaceutical, food and biodiesel industries and oil recovery enhancement through CO 2 flooding. In the present work, it is investigated how the CPA EoS (Cubic-Plus-Association equation of state) can be used for an adequate description of the VLE of an extensive series of CO 2 binary systems containing n -alkanes, n -alcohols, esters and n -acids, in a broad range of temperatures and pressures. These families constitute a series of non-self associating, associating and cross-associating components whose potential associative interactions with CO 2 are evaluated here. A detailed investigation regarding the differing behavior of CO 2 depending on the nature of the second component and how the CPA EoS can best describe them is presented here, namely explicitly considering the CO 2 association and also evaluating also its different association schemes. It will be shown that it is important to consider CO 2 self- and cross-association to describe the VLE of n -alkane and small alcohol/CO 2 systems. However, it is not necessary to consider CO 2 association when dealing with systems of heavy alcohols, esters or acids. The CPA EoS provides very good results for the extensive range of CO 2 binary systems considered here using, for most of them, single, small, temperature independent, positive and chain length dependent binary interaction parameters.

[1]  F. Cansell,et al.  CO2−Ethanol Interaction Studied by Vibrational Spectroscopy in Supercritical CO2 , 2004 .

[2]  S. Kim,et al.  Vapor-liquid equilibria for binary mixtures of CO2 with 2-methyl-2-propanol, 2-methyl-2-butanol, octanoic acid, and decanoic acid at temperatures from 313.15 K to 353.15 K and pressures from 3 MPa to 24 MPa , 2001 .

[3]  F. Orr,et al.  Carbon dioxide flooding for enhanced oil recovery: Promise and problems , 1982 .

[4]  J. Coutinho,et al.  Phase Equilibria of Ester + Alcohol Systems and Their Description with the Cubic-Plus-Association Equation of State , 2010 .

[5]  K. D. Luks,et al.  Liquid-liquid-vapor immiscibility limits in carbon dioxide + n-paraffin mixtures , 1985 .

[6]  R. L. Robinson,et al.  Solubilities of carbon dioxide in heavy normal paraffins (C20−C44) at pressures to 9.6 MPa and temperatures from 323 to 423 K , 1985 .

[7]  R. Robinson,et al.  Vapor-liquid phase equilibrium for carbon dioxide-n-hexane at 40, 80, and 120 .degree.C , 1981 .

[8]  Danielle Barth,et al.  Phase Equilibria Measurements and Modeling of EPA and DHA Ethyl Esters in Supercritical Carbon Dioxide , 2001 .

[9]  Yan-Ping Chen,et al.  Vapor-liquid equilibria of carbon dioxide with isopropyl acetate, diethyl carbonate and ethyl butyrate at elevated pressures , 2005 .

[10]  Y. Danten,et al.  Vibrational Spectra of CO2-Electron Donor−Acceptor Complexes from ab Initio , 2002 .

[11]  M. Michelsen,et al.  Application of the Cubic-Plus-Association (CPA) Equation of State to Cross-Associating Systems , 2005 .

[12]  Jimmy A. López,et al.  Phase equilibrium calculations for carbon dioxide + n-alkanes binary mixtures with the Wong–Sandler mixing rules , 2006 .

[13]  E. Ali,et al.  Solubility of CO2 in some heavy alcohols and correlation of fluid phase equilibrium , 2003 .

[14]  Chiehming J. Chang,et al.  A new apparatus for the determination of P–x–y diagrams and Henry's constants in high pressure alcohols with critical carbon dioxide , 1998 .

[15]  L. A. Galicia-Luna,et al.  New isothermal vapor–liquid equilibria for the CO2 + n-nonane, and CO2 + n-undecane systems , 2007 .

[16]  Xiaoyan Ji,et al.  SAFT1-RPM Approximation Extended to Phase Equilibria and Densities of CO2−H2O and CO2−H2O−NaCl Systems , 2005 .

[17]  Dimitrios P. Tassios,et al.  An Equation of State for Associating Fluids , 1996 .

[18]  Ralf Dohrn,et al.  High-pressure fluid-phase equilibria: Experimental methods and systems investigated (1988–1993) , 1995 .

[19]  M. Michelsen,et al.  Modeling phase equilibria of alkanols with the simplified PC-SAFT equation of state and generalized pure compound parameters , 2007 .

[20]  M. Michelsen,et al.  Application of the cubic-plus-association equation of state to mixtures with polar chemicals and high pressures , 2006 .

[21]  J. E. Coon,et al.  An equation of state for carboxylic acids , 1993 .

[22]  M. Mendes,et al.  Phase equilibria of oleic, palmitic, stearic, linoleic and linolenic acids in supercritical CO2. , 2009 .

[23]  M. Michelsen,et al.  Ten Years with the CPA (Cubic-Plus-Association) Equation of State. Part 2. Cross-Associating and Multicomponent Systems , 2006 .

[24]  D. Robinson,et al.  Equilibrium-phase properties of n-pentane-carbon dioxide system , 1973 .

[25]  Josep C. Pàmies,et al.  Vapor-Liquid Equilibrium of Carbon Dioxide-Perfluoroalkane Mixtures: Experimental Data and SAFT Modeling , 2006 .

[26]  Masahiro Kato,et al.  Solubility of carbon dioxide in pentadecane, hexadecane, and pentadecane + hexadecane , 1993 .

[27]  K. Johnston,et al.  Solubilization of Biomolecules in Carbon Dioxide Based Supercritical Fluids , 1986, Biotechnology progress.

[28]  G. Kontogeorgis,et al.  An interpretation of the behavior of EoS/GE models for asymmetric systems , 2000 .

[29]  Ioannis N. Tsimpanogiannis,et al.  Thermodynamic modeling of the vapor–liquid equilibrium of the CO2/H2O mixture , 2009 .

[30]  João A. P. Coutinho,et al.  Prediction of Water Solubility in Biodiesel with the CPA Equation of State , 2008 .

[31]  J. Gross,et al.  Modeling the phase equilibria of hydrogen sulfide and carbon dioxide in mixture with hydrocarbons and water using the PCP-SAFT equation of state , 2010 .

[32]  J. D. Hemptinne,et al.  Modeling Phase Equilibrium of H2 + n-Alkane and CO2 + n-Alkane Binary Mixtures Using a Group Contribution Statistical Association Fluid Theory Equation of State (GC−SAFT−EOS) with a kij Group Contribution Method , 2006 .

[33]  B. Kirchner,et al.  Structural and thermodynamic properties of fluid carbon dioxide from a new ab initio potential energy surface , 1998 .

[34]  Jeffrey H. Williams,et al.  The molecular electric quadrupole moment and solid-state architecture , 1993 .

[35]  Michael R. Nelson,et al.  Ab Initio Calculations on CO 2 Binding to Carbonyl Groups , 1998 .

[36]  I. Marrucho,et al.  Description of the mutual solubilities of fatty acids and water with the CPA EoS , 2009 .

[37]  E. Stenby,et al.  Predictions of three-phase regions in CO2-oil mixtures , 1995 .

[38]  K. Arai,et al.  Vapour—liquid equilibria for binary mixtures of carbon dioxide and fatty acid methyl esters , 1989 .

[39]  Ireneo Kikic,et al.  High pressure fluid phase equilibria : experimental methods and systems investigated (1978-1987) , 1990 .

[40]  K. D. Luks,et al.  Phase equilibria behavior of the systems carbon dioxide + n-dotriacontane and carbon dioxide + n-docosane , 1984 .

[41]  E. Voutsas,et al.  Prediction of phase equilibria in water/alcohol/alkane systems , 1999 .

[42]  Keith E. Gubbins,et al.  SAFT prediction of vapour-liquid equilibria of mixtures containing carbon dioxide and aqueous monoethanolamine or diethanolamine , 1999 .

[43]  A. Haghtalab,et al.  Vapor–liquid equilibria of asymmetrical systems using UNIFAC-NRF group contribution activity coefficient model , 2010 .

[44]  J. Prausnitz,et al.  High-pressure vapor-liquid equilibria for carbon dioxide/n-decane, carbon dioxide/tetralin, and carbon dioxide/n-decane/tetralin at 71.1 and 104.4.degree. C , 1990 .

[45]  J. Coutinho,et al.  On the Nonideality of CO2 Solutions in Ionic Liquids and Other Low Volatile Solvents , 2010 .

[46]  Fuan‐Nan Tsai,et al.  Solubility of carbon dioxide in n-tetracosane and in n-dotriacontane , 1990 .

[47]  I. Marrucho,et al.  Surface tension of chain molecules through a combination of the gradient theory with the CPA EoS , 2008 .

[48]  M. McHugh,et al.  Phase Behavior and Modeling of Supercritical Carbon Dioxide−Organic Acid Mixtures , 2000 .

[49]  Xiao-Sen Li,et al.  Investigation of vapor-liquid equilibria for supercritical carbon dioxide and hydrocarbon mixtures by perturbed-chain statistical associating fluid theory , 2006 .

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

[51]  F. Mutelet,et al.  Predicting the phase equilibria of CO2+hydrocarbon systems with the PPR78 model (PR EOS and kij calculated through a group contribution method) , 2008 .

[52]  Saul B. Suslick,et al.  CO2 sequestration through enhanced oil recovery in a mature oil field , 2009 .

[53]  M. Michelsen,et al.  Ten Years with the CPA (Cubic-Plus-Association) Equation of State. Part 1. Pure Compounds and Self-Associating Systems , 2006 .

[54]  I. Polishuk,et al.  Estimation of Liquid−Liquid−Vapor Equilibria Using Predictive EOS Models. 1. Carbon Dioxide−n-Alkanes , 2003 .

[55]  I. Polishuk,et al.  Simultaneous prediction of the critical and sub-critical phase behavior in mixtures using equations of state II. Carbon dioxide–heavy n-alkanes , 2001 .

[56]  Yan Li,et al.  Prediction of Vapor−Liquid Equilibrium at High Pressure Using a New Excess Free Energy Mixing Rule Coupled with the Original UNIFAC Method and the SRK Equation of State , 2009 .

[57]  K. Gasem,et al.  Equilibrium phase compositions, phase densities, and interfacial tensions for CO sub 2 + hydrocarbon systems; CO sub 2 + n-butane + n-decane , 1990 .

[58]  Poovathinthodiyil Raveendran,et al.  Cooperative C-H...O hydrogen bonding in CO(2)-Lewis base complexes: implications for solvation in supercritical CO(2). , 2002, Journal of the American Chemical Society.

[59]  M. Lísal,et al.  Effect of short- and long-range forces on the properties of fluids. III. Dipolar and quadrupolar fluids , 2001 .

[60]  João A. P. Coutinho,et al.  Binary interaction parameters for nonpolar systems with cubic equations of state: a theoretical approach 1. CO2/hydrocarbons using SRK equation of state , 1994 .

[61]  K. Gasem,et al.  Equilibrium phase compositions, phase densities, and interfacial tensions for carbon dioxide + hydrocarbon systems. 5. Carbon dioxide + n-tetradecane , 1985 .

[62]  E. Neau,et al.  High-pressure apparatus for phase equilibria studies: solubility of fatty acid esters in supercritical CO2 , 1999 .

[63]  E. Ibáñez,et al.  Deacidification of olive oil by countercurrent supercritical carbon dioxide extraction: Experimental and thermodynamic modeling , 2009 .

[64]  António J. Queimada,et al.  Phase equilibria of glycerol containing systems and their description with the Cubic-Plus-Association (CPA) Equation of State , 2009 .

[65]  Amparo Galindo† and,et al.  Theoretical Examination of the Global Fluid Phase Behavior and Critical Phenomena in Carbon Dioxide + n-Alkane Binary Mixtures , 2002 .

[66]  A. Teja,et al.  Vapor-Liquid Equilibria in the Carbon Dioxide + 1-Propanol System , 1995 .

[67]  I. Polishuk,et al.  Prediction of phase equilibria in the systems carbon dioxide (1)―fatty acids (2) by two cubic EOS models and classical mixing rules without binary adjustable parameters , 2010 .

[68]  K. Cheng,et al.  Vapor–liquid equilibrium of carbon dioxide with ethyl caproate, ethyl caprylate and ethyl caprate at elevated pressures , 2004 .

[69]  F. Leder,et al.  This time it's different: An inevitable decline in world petroleum production will keep oil product prices high, causing military conflicts and shifting wealth and power from democracies to authoritarian regimes , 2008 .

[70]  S. Longelin,et al.  Transient dimer formation in supercritical carbon dioxide as seen from Raman scattering. , 2008, The Journal of chemical physics.

[71]  Jean-Charles de Hemptinne,et al.  Modeling Phase Equilibria of Asymmetric Mixtures Using a Group-Contribution SAFT (GC-SAFT) with a kij Correlation Method Based on London’s Theory. 1. Application to CO2 + n-Alkane, Methane + n-Alkane, and Ethane + n-Alkane Systems , 2008 .

[72]  E. Voutsas,et al.  An evaluation of the performance of the Cubic-Plus-Association equation of state in mixtures of non-polar, polar and associating compounds: Towards a single model for non-polymeric systems , 2007 .

[73]  Ralf Dohrn,et al.  High-pressure fluid phase equilibria , 2002 .

[74]  S. Sandler,et al.  Vapor-liquid equilibria and critical points of the CO2 + 1-hexanol and CO2 + 1-heptanol systems , 2003 .

[75]  P. Englezos,et al.  Vapor−Liquid Equilibrium of Systems Containing Alcohols Using the Statistical Associating Fluid Theory Equation of State , 2003 .

[76]  G. Kontogeorgis,et al.  Multicomponent phase equilibrium calculations for water–methanol–alkane mixtures , 1999 .

[77]  João A. P. Coutinho,et al.  Prediction of near and supercritical fatty acid ester + alcohol systems with the CPA EoS , 2010 .

[78]  Joachim Gross,et al.  A density functional theory for vapor-liquid interfaces using the PCP-SAFT equation of state. , 2009, The Journal of chemical physics.

[79]  M. Michelsen,et al.  Solvation Phenomena in Association Theories with Applications to Oil & Gas and Chemical Industries , 2008 .

[80]  Kunio Arai,et al.  Isothermal vapor-liquid equilibrium data for binary systems at high pressures: carbon dioxide-methanol, carbon dioxide-ethanol, carbon dioxide-1-propanol, methane-ethanol, methane-1-propanol, ethane-ethanol, and ethane-1-propanol systems , 1990 .

[81]  M. Caude,et al.  L'extraction en phase supercritique à l'échelle analytique : principe, mise en œuvre et applications , 1992 .

[82]  Chiehming J. Chang,et al.  Vapor-liquid equilibria and densities of CO2 with four unsaturated fatty acid esters at elevated pressures , 2005 .

[83]  C. Mai,et al.  Solubility of carbon dioxide in 1-tetradecanol, 1-hexadecanol, and 1-octadecanol , 1994 .

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

[85]  H. Cramail,et al.  On the perturbation of the intramolecular H-bond in diols by supercritical CO2: a theoretical and spectroscopic study. , 2007, The journal of physical chemistry. A.

[86]  S. Longelin,et al.  Raman spectroscopy of CO2–acetone and CO2–ethanol complexes , 2005 .

[87]  R. Dohrn,et al.  High-pressure fluid-phase equilibria: Experimental methods and systems investigated (2000–2004) , 2010 .

[88]  C. A. Lockemann.  High-pressure phase equilibria and densities of the binary mixtures carbon dioxide-oleic acid, carbon dioxide-methyl myristate, and carbon dioxide-methyl palmitate and of the ternary mixture carbon dioxide-methyl myristate-methyl palmitate , 1994 .

[89]  J. García,et al.  Phase Equilibria, PVT Behavior, and Critical Phenomena in Carbon Dioxide + n-Alkane Mixtures Using the Perturbed-Chain Statistical Associating Fluid Theory Approach , 2004 .

[90]  A. A. Refaat,et al.  Different techniques for the production of biodiesel from waste vegetable oil , 2010 .

[91]  F. Gironi,et al.  Separation of fish oils ethyl esters by means of supercritical carbon dioxide: Thermodynamic analysis and process modelling , 2006 .

[92]  D. Geanǎ,et al.  High-Pressure Vapor−Liquid Equilibria in the System Carbon Dioxide + 1-Butanol at Temperatures from (293.15 to 324.15) K , 2004 .

[93]  M. Donohue,et al.  Supercritical phase behavior: The entrainer effect , 1987 .

[94]  H. Schlegel,et al.  Ab initio study of the CO2 dimer and the CO2 ion complexes (CO2)2+ and (CO2)3+ , 1987 .

[95]  D. Geanǎ,et al.  Investigation of phase equilibria in the ternary system carbon dioxide + 1-heptanol + n-pentadecane , 2007 .

[96]  José O. Valderrama,et al.  The state of the cubic equations of state , 2003 .

[97]  Carlos A. Cardona,et al.  Parameters estimation and VLE calculation in asymmetric binary mixtures containing carbon dioxide + n-alkanols , 2009 .

[98]  G. Soave,et al.  Vapor–liquid equilibria of systems containing acetic acid and gaseous components. Measurements and calculations by a cubic equation of state , 1998 .

[99]  Fèlix Llovell,et al.  Global fluid phase equilibria and critical phenomena of selected mixtures using the crossover soft-SAFT equation. , 2006, The journal of physical chemistry. B.

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

[101]  Abbas Firoozabadi,et al.  Cubic‐plus‐association equation of state for water‐containing mixtures: Is “cross association” necessary? , 2009 .

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

[103]  S. Sandler,et al.  Vapor–liquid equilibria and critical points for the carbon dioxide +1-pentanol and carbon dioxide +2-pentanol systems at temperatures from 332 to 432 K , 2002 .

[104]  João A. P. Coutinho,et al.  Mutual solubilities of hydrocarbons and water with the CPA EoS , 2007 .

[105]  M. Michelsen,et al.  Application of the Cubic-Plus-Association (CPA) Equation of State to Complex Mixtures with Aromatic Hydrocarbons , 2006 .

[106]  I. Nieuwoudt,et al.  Measurement of phase equilibria of supercritical carbon dioxide and paraffins , 2002 .

[107]  E. Voutsas,et al.  Thermodynamic modeling of the water + acetic acid + CO2 system : The importance of the number of association sites of water and of the nonassociation contribution for the CPA and SAFT-type models , 2007 .