Modélisation thermodynamique des mélanges complexes
Axe de recherche :
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Thermodynamique des mélanges (voir les détails sur la page dédiée)
Publications scientifiques au M2P2
2020
Isabelle Raspo, Evelyne Neau. An empirical correlation for the relative permittivity of liquids in a wide temperature range: application to the modeling of electrolyte systems with a GE/EoS approach.. Fluid Phase Equilibria, Elsevier, 2020, 506, pp.112371. ⟨10.1016/j.fluid.2019.112371⟩. ⟨hal-02325903⟩ Plus de détails...
Relative permittivity, also known as static dielectric constant, is a key property of solvents in electrolyte solutions. It strongly influences the solubility of solutes and, therefore, it can be used as a predictive tool in chemical engineering processes. Relative permittivity also plays an essential role in the modeling of phase equilibria of electrolyte systems, since it is involved in the Debye-Hückel model and in the Mean Spherical Approximation, commonly used to represent long-range interactions between ions. In this paper, we propose a new temperature-dependent correlation for the relative permittivity of liquid water, methanol and ethanol, valid in a wide temperature range, including very high temperatures. Comparison with other literature equations evidenced that the main interest of the proposed correlation is to allow satisfactory predictions of the relative permittivity, not only in the range of validity of other literature models, but also in the high temperature domain, including supercritical temperatures for water. The new correlation is then used with the NRTL-PRA EoS to predict vapor pressure of water with several salts, including single electrolytes and two-salts mixtures; it must be noted that the modeling presented in this work is relevant for any GE/EoS model, since in this case (binary interactions between water and ions being equal to zero), the excess Gibbs energy reduces to the Long-Range term derived from the Pitzer-Debye-Hückel model. A temperature-dependent correction of the solvent relative permittivity is proposed to account for its dependence on ion mole fraction in this Long-Range term. Results thus obtained show that this correction leads to an accurate prediction both: for vapor pressures of aqueous electrolyte solutions in a very wide temperature domain and for the modeling of vapor-liquid equilibria of methanol-water and ethanol-water mixtures with several salts.
Isabelle Raspo, Evelyne Neau. An empirical correlation for the relative permittivity of liquids in a wide temperature range: application to the modeling of electrolyte systems with a GE/EoS approach.. Fluid Phase Equilibria, Elsevier, 2020, 506, pp.112371. ⟨10.1016/j.fluid.2019.112371⟩. ⟨hal-02325903⟩
Isabelle Raspo, Evelyne Neau. An empirical correlation for the relative permittivity of liquids in a wide temperature range: application to the modeling of electrolyte systems with a GE/EoS approach.. Fluid Phase Equilibria, Elsevier, In press. ⟨hal-02325903⟩ Plus de détails...
Relative permittivity, also known as static dielectric constant, is a key property of solvents in electrolyte solutions. It strongly influences the solubility of solutes and, therefore, it can be used as a predictive tool in chemical engineering processes. Relative permittivity also plays an essential role in the modeling of phase equilibria of electrolyte systems, since it is involved in the Debye-Hückel model and in the Mean Spherical Approximation, commonly used to represent long-range interactions between ions. In this paper, we propose a new temperature-dependent correlation for the relative permittivity of liquid water, methanol and ethanol, valid in a wide temperature range, including very high temperatures. Comparison with other literature equations evidenced that the main interest of the proposed correlation is to allow satisfactory predictions of the relative permittivity, not only in the range of validity of other literature models, but also in the high temperature domain, including supercritical temperatures for water. The new correlation is then used with the NRTL-PRA EoS to predict vapor pressure of water with several salts, including single electrolytes and two-salts mixtures; it must be noted that the modeling presented in this work is relevant for any GE/EoS model, since in this case (binary interactions between water and ions being equal to zero), the excess Gibbs energy reduces to the Long-Range term derived from the Pitzer-Debye-Hückel model. A temperature-dependent correction of the solvent relative permittivity is proposed to account for its dependence on ion mole fraction in this Long-Range term. Results thus obtained show that this correction leads to an accurate prediction both: for vapor pressures of aqueous electrolyte solutions in a very wide temperature domain and for the modeling of vapor-liquid equilibria of methanol-water and ethanol-water mixtures with several salts.
Isabelle Raspo, Evelyne Neau. An empirical correlation for the relative permittivity of liquids in a wide temperature range: application to the modeling of electrolyte systems with a GE/EoS approach.. Fluid Phase Equilibria, Elsevier, In press. ⟨hal-02325903⟩
Evelyne Neau, Christophe Nicolas, Laurent Avaullée. Extension of the group contribution NRTL-PRA EoS for the modeling of mixtures containing light gases and alcohols with water and salts. Fluid Phase Equilibria, Elsevier, 2018, 458, pp.194-210. ⟨10.1016/j.fluid.2017.09.028⟩. ⟨hal-01703014⟩ Plus de détails...
The offshore exploitation of petroleum fluids in normal conditions of pressure and temperature of transport and in presence of salt water is concerned with the prevention of gas hydrate formation, generally thanks to continuous injection of inhibitors, or punctual injection of methanol in start-up and shut-down operations. Hence, models of interest should provide both, satisfactory phase equilibrium estimations of hydrocarbon and alcohol mixtures with water and reliable predictions of their behavior in presence of salts.
Evelyne Neau, Christophe Nicolas, Laurent Avaullée. Extension of the group contribution NRTL-PRA EoS for the modeling of mixtures containing light gases and alcohols with water and salts. Fluid Phase Equilibria, Elsevier, 2018, 458, pp.194-210. ⟨10.1016/j.fluid.2017.09.028⟩. ⟨hal-01703014⟩
Evelyne Neau, Isabelle Raspo, Joan Escandell. The NRTL-PRA group contribution EoS for the simultaneous prediction of LLE, VLE and hE of hydrocarbon mixtures with associating compounds. Fluid Phase Equilibria, Elsevier, 2016, 427, pp.126-142. ⟨10.1016/j.fluid.2016.06.035⟩. ⟨hal-01369874⟩ Plus de détails...
The goal of this study is to propose a modification of the NRTL-PR EoS for the prediction of phase equilibria and excess enthalpies in mixtures containing methanol with hydrocarbons; indeed, with these systems, the original equation is confronted to many difficulties arising from the simultaneous prediction of liquid-liquid equilibria together with vapor-liquid and enthalpy data. For this purpose, an additional term is included in the EoS excess Gibbs energy, , of the Peng-Robinson equation to account for the self-association of methanol. The resulting NRTL-PRA EoS is successfully used for the prediction of both liquid-liquid and vapor-liquid equilibria, as well as excess enthalpies, in mixtures of methanol with hydrocarbons, light gases and associating compounds. Results are comparable to those obtained with other predictive EoS (VTPR and SAFT), but with the main advantage to predict all thermodynamic properties with a simple cubic equation.
Evelyne Neau, Isabelle Raspo, Joan Escandell. The NRTL-PRA group contribution EoS for the simultaneous prediction of LLE, VLE and hE of hydrocarbon mixtures with associating compounds. Fluid Phase Equilibria, Elsevier, 2016, 427, pp.126-142. ⟨10.1016/j.fluid.2016.06.035⟩. ⟨hal-01369874⟩
Joan Escandell, Isabelle Raspo, Evelyne Neau. Prediction of Solid Polycyclic Aromatic Hydrocarbons Solubility in Water with the NRTL-PR Model. Fluid Phase Equilibria, Elsevier, 2014, 362 (25), pp.87-95. ⟨10.1016/j.fluid.2013.09.009⟩. ⟨hal-00872639⟩ Plus de détails...
The accurate prediction of high pressure phase equilibria is crucial for the development and the design of chemical engineering processes. Among them the modeling of complex systems, such as petroleum fluids with water, has become more and more important with the exploitation of reservoirs in extreme conditions. The aim of this work is to explore the capability of the NRTL-PR model to predict the solubility of solid polycyclic aromatic hydrocarbons in water. For this purpose, we first validate our methodology for fluid phase equilibria predictions of aromatic hydrocarbons and gas (CO2, C2H6) mixtures. Finally, we consider the prediction of the solid solubility of PAH in water, by fitting group parameters either only on SLE data or on both LLE and SLE data of aromatic hydrocarbon-water binary systems.
Joan Escandell, Isabelle Raspo, Evelyne Neau. Prediction of Solid Polycyclic Aromatic Hydrocarbons Solubility in Water with the NRTL-PR Model. Fluid Phase Equilibria, Elsevier, 2014, 362 (25), pp.87-95. ⟨10.1016/j.fluid.2013.09.009⟩. ⟨hal-00872639⟩
Joan Escandell, Evelyne Neau, Christophe Nicolas. A new formulation of the predictive NRTL-PR model in terms of k(ij) ă mixing rules. Extension of the group contributions for the modeling of ă hydrocarbons in the presence of associating compounds. Fluid Phase Equilibria, Elsevier, 2011, 301 (1), pp.80-97. ⟨10.1016/j.fluid.2010.11.009⟩. ⟨hal-01464747⟩ Plus de détails...
A generalized NRTL model was previously proposed for the modeling of non ă ideal systems and was extended to the prediction of phase equilibria ă under pressure according to the cubic NRTL-PR EoS. In this work, the ă model is reformulated with a predictive k(ij) temperature and ă composition dependent mixing rule and new interaction parameters are ă proposed between permanent gases, ethane and nitrogen with hydrocarbons, ă ethane with water and ethylene glycol. Results obtained for excess ă enthalpies, liquid-vapor and liquid-liquid equilibria are compared with ă those provided by the literature models, such as VTPR, PPR78, CPA and ă SRKm. A wide variety of mixtures formed by very asymmetric compounds, ă such as hydrocarbons, water and ethylene glycols are considered and ă special attention is paid to the evolution of k(ij) with respect to mole ă fractions and temperature. (C) 2010 Elsevier B.V. All rights reserved.
Joan Escandell, Evelyne Neau, Christophe Nicolas. A new formulation of the predictive NRTL-PR model in terms of k(ij) ă mixing rules. Extension of the group contributions for the modeling of ă hydrocarbons in the presence of associating compounds. Fluid Phase Equilibria, Elsevier, 2011, 301 (1), pp.80-97. ⟨10.1016/j.fluid.2010.11.009⟩. ⟨hal-01464747⟩
Evelyne Neau, Joan Escandell, Isabelle Raspo. A generalized reference state at constant volume for the prediction of phase equilibria from low pressure model parameters: application to size-asymmetric systems and to the Wong-Sandler mixing rule. Chemical Engineering Science, Elsevier, 2011, 66 (18), pp.4148-4156. ⟨10.1016/j.ces.2011.05.043⟩. ⟨hal-01023163⟩ Plus de détails...
This paper describes an EoS/GE approach based on cubic equations of state making reference to low pressure GE models derived from the lattice fluid theory of Guggenheim. The proposed method does not present the theoretical problems encountered with the literature reference states (infinite pressure of Huron-Vidal, zero pressure of Michelsen and constant packing fraction of Péneloux), namely the description of the alpha function with combinatorial terms derived from both the excess Gibbs energy model and the EoS. The main advantage of the proposed method is to successfully account for the size-asymmetry of mixture components and to improve the results obtained with the Wong-Sandler mixing rule. Comparisons are performed with the MHV1, LCVM and the original Wong-Sandler approach at infinite pressure.
Evelyne Neau, Joan Escandell, Isabelle Raspo. A generalized reference state at constant volume for the prediction of phase equilibria from low pressure model parameters: application to size-asymmetric systems and to the Wong-Sandler mixing rule. Chemical Engineering Science, Elsevier, 2011, 66 (18), pp.4148-4156. ⟨10.1016/j.ces.2011.05.043⟩. ⟨hal-01023163⟩
Evelyne Neau, Joan Escandell, Christophe Nicolas. Modeling of highly nonideal systems: 1. A generalized version of the NRTL equation for the description of low-pressure equilibria. Industrial and engineering chemistry research, American Chemical Society, 2010, 49 (16), pp.7580-7588. ⟨10.1021/ie100121c⟩. ⟨hal-01025255⟩ Plus de détails...
The topic of the present work is the development of a simple model for the description of phase equilibria occurring in nonideal systems, such as those containing size-asymmetric components or mixtures made of polar or associating compounds with hydrocarbons, that are capable of strong demixing. The generalized NRTL model presented in this first part derives from the lattice two-fluid theory and differs from the original model by considering the size asymmetry of mixture components; results obtained for the modeling of phase equilibria in hydrocarbon, polar, and highly immiscible systems are compared with other literature models, such as the van Laar, NRTL, and UNIQUAC models. In the second part of this work, this model is associated with the Peng−Robinson EoS using the EoS/GE approach based on a generalized reference state, and a new group contribution is proposed for the prediction of the binary interaction parameters.
Evelyne Neau, Joan Escandell, Christophe Nicolas. Modeling of highly nonideal systems: 1. A generalized version of the NRTL equation for the description of low-pressure equilibria. Industrial and engineering chemistry research, American Chemical Society, 2010, 49 (16), pp.7580-7588. ⟨10.1021/ie100121c⟩. ⟨hal-01025255⟩
Journal: Industrial and engineering chemistry research
Evelyne Neau, Joan Escandell, Christophe Nicolas. Modeling of highly nonideal systems: 2. Prediction of high pressure phase equilibria with the group contribution NRTL-PR EoS. Industrial and engineering chemistry research, American Chemical Society, 2010, 49 (16), pp.7589-7596. ⟨10.1021/ie101266x⟩. ⟨hal-01025263⟩ Plus de détails...
The purpose of this study is to propose a simple cubic equation of state for the prediction of phase equilibria in highly non ideal systems. The NRTL-PR equation of state is based on the association of the Peng−Robinson EoS and the generalized NRTL model developed in the first part of this work. This model, which derives from the lattice two-fluid theory, was specially developed to take account for the differences in size and shape between mixture components. The main advantage of the resulting NRTL-PR equation of state is to yield a simple and predictive model, depending on very few interaction parameters. In addition, it also allows satisfactory predictions of excess enthalpies, liquid−vapor and liquid−liquid equilibria occurring in mixtures formed by very asymmetric compounds, such as hydrocarbons, water, and ethylene glycols.
Evelyne Neau, Joan Escandell, Christophe Nicolas. Modeling of highly nonideal systems: 2. Prediction of high pressure phase equilibria with the group contribution NRTL-PR EoS. Industrial and engineering chemistry research, American Chemical Society, 2010, 49 (16), pp.7589-7596. ⟨10.1021/ie101266x⟩. ⟨hal-01025263⟩
Journal: Industrial and engineering chemistry research
Most of the models proposed in literature for binary diffusion coefficients of solids in supercritical fluids are restricted to infinite dilution; this can be explained by the fact that most of experimental data are performed in the dilute range. However some industrial processes, such as supercritical fluid separation, operate at finite concentration for complex mixtures. In this case, the concentration dependence of diffusion coefficients must be considered, especially near the upper critical endpoint (UCEP) where a strong decrease of diffusion coefficients was experimentally observed. In order to represent this slowing down, a modified version of the Darken equation was proposed in literature for naphthalene in supercritical carbon dioxide. In this paper, the conditions of application of such a modelling are investigated. In particular, we focus on the order of magnitude of the solubility of the solid and on the vicinity of the critical endpoint. Various equations proposed in literature for the modelling of the infinite dilution diffusion coefficients of the solutes are also compared. Ten binary mixtures of solids with supercritical carbon dioxide were considered for this purpose.
Isabelle Raspo, Christophe Nicolas, Evelyne Neau, Sofiane Meradji. Diffusion coefficients of solids in supercritical carbon dioxide: Modelling of near critical behaviour. Fluid Phase Equilibria, Elsevier, 2008, 263 (2), pp.214-222. ⟨10.1016/j.fluid.2007.09.025⟩. ⟨hal-01139192⟩
Christophe Nicolas, Evelyne Neau, Sofiane Meradji, Isabelle Raspo. The Sanchez-Lacombe lattice fluid model for the modeling of solids in supercritical fluids. Fluid Phase Equilibria, Elsevier, 2005, 232 (1-2), pp.219-229. ⟨10.1016/j.fluid.2005.03.015⟩. ⟨hal-00846093⟩ Plus de détails...
The Sanchez-Lacombe equation of state is known to describe the thermodynamic properties of molecular fluids of arbitrary size, especially polymer-solvent phase behavior. However, it is rarely used for modeling solid-supercritical fluid equilibria. In this work, it is shown that a proper estimation of the EoS characteristic parameters together with a thermodynamically consistent expression of fugacity coefficients allows a satisfactory correlation of the solubility of solids in the supercritical phase. Binary mixtures containing carbon dioxide, ethane, ethylene and xenon were considered for this purpose. In a first step, the consistency of experimental data was checked using variance analysis. Then, different mixing rules were considered and results compared with those obtained with the Peng-Robinson equation. Finally, the lower and upper boundaries of the solid-liquid-vapor regions (LCEP and UCEP) were also determined and compared with experimental values.
Christophe Nicolas, Evelyne Neau, Sofiane Meradji, Isabelle Raspo. The Sanchez-Lacombe lattice fluid model for the modeling of solids in supercritical fluids. Fluid Phase Equilibria, Elsevier, 2005, 232 (1-2), pp.219-229. ⟨10.1016/j.fluid.2005.03.015⟩. ⟨hal-00846093⟩
Laurent Avaullee, Evelyne Neau, Jean-Noël Jaubert. Thermodynamic modeling for petroleum fluids II. Prediction of PVT properties of oils and gases by fitting one or two parameters to the saturation pressures of reservoir fluids. Fluid Phase Equilibria, Elsevier, 1997, 139 (1-2), pp.171 - 203. ⟨10.1016/s0378-3812(97)00170-2⟩. ⟨hal-01705902⟩ Plus de détails...
Laurent Avaullee, Evelyne Neau, Jean-Noël Jaubert. Thermodynamic modeling for petroleum fluids II. Prediction of PVT properties of oils and gases by fitting one or two parameters to the saturation pressures of reservoir fluids. Fluid Phase Equilibria, Elsevier, 1997, 139 (1-2), pp.171 - 203. ⟨10.1016/s0378-3812(97)00170-2⟩. ⟨hal-01705902⟩
Laurent Avaullee, Laurent Trassy, Evelyne Neau, Jean Noël Jaubert. Thermodynamic modeling for petroleum fluids I. Equation of state and group contribution for the estimation of thermodynamic parameters of heavy hydrocarbons. Fluid Phase Equilibria, Elsevier, 1997, 139 (1-2), pp.155 - 170. ⟨10.1016/s0378-3812(97)00168-4⟩. ⟨hal-01705903⟩ Plus de détails...
Laurent Avaullee, Laurent Trassy, Evelyne Neau, Jean Noël Jaubert. Thermodynamic modeling for petroleum fluids I. Equation of state and group contribution for the estimation of thermodynamic parameters of heavy hydrocarbons. Fluid Phase Equilibria, Elsevier, 1997, 139 (1-2), pp.155 - 170. ⟨10.1016/s0378-3812(97)00168-4⟩. ⟨hal-01705903⟩
Jean-Noeel Jaubert, Evelyne Neau. Characterization of Heavy Oils. 2. Definition of a Significant Characterizing Parameter To Ensure the Reliability of Predictive Methods for PVT Calculations. Industrial and engineering chemistry research, American Chemical Society, 1995, 34 (5), pp.1873 - 1881. ⟨10.1021/ie00044a039⟩. ⟨hal-01703515⟩ Plus de détails...
Jean-Noeel Jaubert, Evelyne Neau. Characterization of Heavy Oils. 2. Definition of a Significant Characterizing Parameter To Ensure the Reliability of Predictive Methods for PVT Calculations. Industrial and engineering chemistry research, American Chemical Society, 1995, 34 (5), pp.1873 - 1881. ⟨10.1021/ie00044a039⟩. ⟨hal-01703515⟩
Journal: Industrial and engineering chemistry research
Jean-Noeel Jaubert, Evelyne Neau, Andre Peneloux, Catherine Fressigné, Alain Fuchs. Pressure, Volume, and Temperature Calculations on an Indonesian Crude Oil Using Detailed NMR Analysis or a Predictive Method To Assess the Properties of the Heavy Fractions. Industrial and engineering chemistry research, American Chemical Society, 1995, 34 (2), pp.640-655. ⟨10.1021/ie00041a026⟩. ⟨hal-01703512⟩ Plus de détails...
Jean-Noeel Jaubert, Evelyne Neau, Andre Peneloux, Catherine Fressigné, Alain Fuchs. Pressure, Volume, and Temperature Calculations on an Indonesian Crude Oil Using Detailed NMR Analysis or a Predictive Method To Assess the Properties of the Heavy Fractions. Industrial and engineering chemistry research, American Chemical Society, 1995, 34 (2), pp.640-655. ⟨10.1021/ie00041a026⟩. ⟨hal-01703512⟩
Journal: Industrial and engineering chemistry research
Evelyne Neau, Jean-Noël Jaubert, Marek Rogalski. Characterization of heavy oils. Industrial and engineering chemistry research, American Chemical Society, 1993, 32 (6), pp.1196 - 1203. ⟨10.1021/ie00018a027⟩. ⟨hal-01705918⟩ Plus de détails...
Evelyne Neau, Jean-Noël Jaubert, Marek Rogalski. Characterization of heavy oils. Industrial and engineering chemistry research, American Chemical Society, 1993, 32 (6), pp.1196 - 1203. ⟨10.1021/ie00018a027⟩. ⟨hal-01705918⟩
Journal: Industrial and engineering chemistry research