TY - JOUR
T1 - On the predictive capabilities of CPA for applications in the chemical industry: Mulficomponent mixtures containing methyl-methacrylate, dimethyl-ether or acetic acid
AU - Tsivintzelis, Ioannis
AU - Kontogeorgis, Georgios
PY - 2014
Y1 - 2014
N2 - The predictive performance of the CPA (Cubic-Plus-Association) equation of state for applications relevant to the chemical industry is illustrated in this work. Three such applications inspired by industrial requests/interest are illustrated here, all of which involve aqueous multicomponent mixtures exhibiting vapor-liquid (VLE) and/or liquid-liquid (LLE) equilibrium. The first two cases include mixtures of methyl-methacrylate with acetone or methanol and dimethyl-ether with ethanol, respectively. In these two cases, the classical form of CPA is used. The third case involves aqueous mixtures with acetic acid, esters, ethers and alcohols, and in this case for water-acetic acid the CPA-Huron Vidal (CPA-HV) version of the model is used. For the latter binary mixture, new CPA-HV binary parameter sets are estimated using, among others, data for activity coefficients at infinite dilutions. The modeling approach is similar in all three cases, i.e. the binary parameters are solely fitted to binary data and thus all multicomponent calculations are considered predictions. It is shown that CPA correlations for binary systems are excellent in all cases using temperature independent parameters except for the acetic acid-water system for which different parameter sets at different temperatures can be recommended. Even with the use of CPA-HV mixing rules, modeling of the acetic acid-water system with few interaction parameters remains a challenging task. Excellent simultaneous VLE and LLE correlation is obtained for complex systems such as aqueous mixtures with ethers and esters. The multicomponent results are, with a few exceptions, very satisfactory, especially for the vapor-liquid equilibrium cases. For the demanding aqueous acetic acid-water containing systems, one parameter set is recommended at the end for modeling ternary or multicomponent mixtures containing acetic acid and water.
AB - The predictive performance of the CPA (Cubic-Plus-Association) equation of state for applications relevant to the chemical industry is illustrated in this work. Three such applications inspired by industrial requests/interest are illustrated here, all of which involve aqueous multicomponent mixtures exhibiting vapor-liquid (VLE) and/or liquid-liquid (LLE) equilibrium. The first two cases include mixtures of methyl-methacrylate with acetone or methanol and dimethyl-ether with ethanol, respectively. In these two cases, the classical form of CPA is used. The third case involves aqueous mixtures with acetic acid, esters, ethers and alcohols, and in this case for water-acetic acid the CPA-Huron Vidal (CPA-HV) version of the model is used. For the latter binary mixture, new CPA-HV binary parameter sets are estimated using, among others, data for activity coefficients at infinite dilutions. The modeling approach is similar in all three cases, i.e. the binary parameters are solely fitted to binary data and thus all multicomponent calculations are considered predictions. It is shown that CPA correlations for binary systems are excellent in all cases using temperature independent parameters except for the acetic acid-water system for which different parameter sets at different temperatures can be recommended. Even with the use of CPA-HV mixing rules, modeling of the acetic acid-water system with few interaction parameters remains a challenging task. Excellent simultaneous VLE and LLE correlation is obtained for complex systems such as aqueous mixtures with ethers and esters. The multicomponent results are, with a few exceptions, very satisfactory, especially for the vapor-liquid equilibrium cases. For the demanding aqueous acetic acid-water containing systems, one parameter set is recommended at the end for modeling ternary or multicomponent mixtures containing acetic acid and water.
KW - Equations of state
KW - CPA
KW - Modeling
KW - Chemicals
KW - Acetic acid
KW - Water
U2 - 10.1016/j.cherd.2014.03.011
DO - 10.1016/j.cherd.2014.03.011
M3 - Journal article
VL - 92
SP - 2947
EP - 2969
JO - Chemical Engineering Research & Design
JF - Chemical Engineering Research & Design
SN - 0263-8762
IS - 12
ER -