Calculation of Multiphase Equilibria Containing Mixed Solvents and Mixed Electrolytes: General Formulation and Case Studies

Ascani, Moreno; Sadowski, Gabriele; Held, Christoph

doi:10.1021/acs.jced.1c00866

Cited by 10 publications

(7 citation statements)

References 86 publications

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“…In this section, our implementation of the algorithm to perform numerical calculation of the CPE is presented. Although the implementation is general, i.e., not limited to a single key reaction and neutral components (see, for instance, our previous work [ 93 , 94 ]), its scope in this work is to calculate the coupled reaction equilibrium and LLE of the two investigated esterification systems. Thus, only systems containing four molecular (i.e., non-charged) components and described by one key reaction are considered.…”

Section: Algorithmic Approachmentioning

confidence: 99%

Simultaneous Predictions of Chemical and Phase Equilibria in Systems with an Esterification Reaction Using PC-SAFT

2023

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The study of chemical reactions in multiple liquid phase systems is becoming more and more relevant in industry and academia. The ability to predict combined chemical and phase equilibria is interesting from a scientific point of view but is also crucial to design innovative separation processes. In this work, an algorithm to perform the combined chemical and liquid–liquid phase equilibrium calculation was implemented in the PC-SAFT framework in order to predict the thermodynamic equilibrium behavior of two multicomponent esterification systems. Esterification reactions involve hydrophobic reacting agents and water, which might cause liquid–liquid phase separation along the reaction coordinate, especially if long-chain alcoholic reactants are used. As test systems, the two quaternary esterification systems starting from the reactants acetic acid + 1-pentanol and from the reactants acetic acid + 1-hexanol were chosen. It is known that both quaternary systems exhibit composition regions of overlapped chemical and liquid–liquid equilibrium. To the best of our knowledge, this is the first time that PC-SAFT was used to calculate simultaneous chemical and liquid–liquid equilibria. All the binary subsystems were studied prior to evaluating the predictive capability of PC-SAFT toward the simultaneous chemical equilibria and phase equilibria. Overall, PC-SAFT proved its excellent capabilities toward predicting chemical equilibrium composition in the homogeneous composition range of the investigated systems as well as liquid–liquid phase behavior. This study highlights the potential of a physical sound model to perform thermodynamic-based modeling of chemical reacting systems undergoing liquid–liquid phase separation.

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Section: Algorithmic Approachmentioning

confidence: 99%

Simultaneous Predictions of Chemical and Phase Equilibria in Systems with an Esterification Reaction Using PC-SAFT

2023

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“…In a consecutive publication, Bülow et al enhanced their framework by including a Bjerrum treatment to account for ion-pairing. A routine to calculate electrolyte multiphase equilibria on the basis of ePC-SAFT “advanced” including multiple distributed ions has been proposed by Ascani et al…”

Section: Introductionmentioning

confidence: 99%

“…In a consecutive publication, Bulow et al 19 enhanced their framework by including a Bjerrum treatment to account for ion-pairing. A routine to calculate electrolyte multiphase equilibria on the basis of ePC-SAFT "advanced" including multiple distributed ions has been proposed by Ascani et al 20 In this work, we investigate the effect of the different cations of the sulfuric components on the LLE. LLE measurements are carried out in a temperature range between 293 and 333 K for the binary system H Motivated by prior work of our group, infrared (IR) spectroscopy is used to acquire multivariate data of the aqueous and organic phases.…”

Section: ■ Introductionmentioning

confidence: 99%

The Effect of Sulfate Electrolytes on the Liquid–Liquid Equilibrium of 2-MTHF/Water/5-HMF: Experimental Study and Thermodynamic Modeling

et al. 2023

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We investigate the influence of sulfate salts and sulfuric acid on the equilibrium behavior of 2-methyltetrahydrofuran (2-MTHF)/H 2 O/5hydroxymethylfurfural (5-HMF). Liquid−liquid equilibrium measurements are performed at atmospheric pressure and in a temperature range of T = (293−333) K. The compositions of the aqueous and organic phases, together with the dissociation state of the sulfate species, are determined with infrared spectroscopy and Indirect Hard Modeling. We show that the addition of the salts Na 2 SO 4 and Li 2 SO 4 results in salting out of 2-MTHF and 5-HMF from the aqueous phase. With increasing temperature, this effect gets less pronounced. In contrast, the addition of H 2 SO 4 does not result in any salting-out behavior. The investigation of the dissociation states shows that H 2 SO 4 dissociates to HSO 4 − while Na 2 SO 4 and Li 2 SO 4 dissociate completely to SO 4 2−. Parameter regression is performed to model the liquid−liquid equilibrium with the electrolyte perturbed-chain statistical associating fluid theory (ePC-SAFT) equation of state. For the analyzed salts, Na 2 SO 4 and Li 2 SO 4 , the performed parameter regression accurately predicts the measurement results. Still, we observe slight deviations between measured values and modeling when predicting the liquid−liquid equilibrium and the liquid density in the presence of sulfuric acid.

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“…2−4 Moreover, methods were developed to describe the simultaneous occurrence of chemical reactions and phase equilibria. 5 Over the past decades, CO 2 solubility has been modeled by many researchers using different approaches, such as Statistical Associating Fluid Theory (SAFT), 6 SAFT-VRE, 7 SAFT-γ Mie, 8 electrolyte Cubic-Plus-Association (e-CPA), 9 or nonrandom two-liquid (NRTL)-Perturbed-Chain (PC)-SAFT. 10 However, all of these approaches are not predictive since they require fit parameters.…”

Section: Introductionmentioning

confidence: 99%

Influence of Solvents and Salts on CO₂ Solubility and the Impact on an Esterification Reaction

Schick,

Chen,

Hellfajer

et al. 2023

J. Chem. Eng. Data

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The influence of solvents and salts on the CO 2 solubility and the impact on esterification reaction kinetics and equilibrium are of particular interest, e.g., for the esterification of acetic acid with ethanol under the influence of CO 2 , N-methyl-2pyrrolidone (NMP), or electrolytes. In this work, the equation of state (EOS) electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC-SAFT advanced) was first applied to predict the CO 2 solubility in solvent mixtures containing NMP and water with additional electrolytes (NaCl, CsCl). New experimental data on the CO 2 solubility in electrolyte solutions were measured by two different static synthetic methods, and the ePC-SAFT predictions matched well with the experimental data. As a result, NMP increased the CO 2 solubility, compared to water as the only solvent, while electrolytes caused a salting-out effect on the CO 2 solubility in all investigated systems. Further, the kinetics and equilibria of the esterification reaction were studied in the presence of CO 2 , NMP, and electrolytes. New data were measured by using a high-pressure autoclave with in situ ATR-FTIR spectroscopy, which enabled real-time monitoring of the kinetic profiles. Therein, CO 2 and NMP showed a negative effect on the kinetics. However, the additional CO 2 in the reaction mixture positively influenced the equilibrium, while NMP had a negative influence. Finally, ePC-SAFT advanced was applied to predict the influence of CO 2 and NMP on both kinetics and equilibrium of ethanol esterification using a thermodynamic activity-based kinetic approach. Therein, the experimental findings were successfully predicted by the model without fitting any model parameter to the experimental data. Ultimately, this approach reduces the experimental effort toward screening most suitable reaction conditions for chemical reactions and screening the influence of other compounds on kinetics and equilibria.

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Calculation of Multiphase Equilibria Containing Mixed Solvents and Mixed Electrolytes: General Formulation and Case Studies

Cited by 10 publications

References 86 publications

Simultaneous Predictions of Chemical and Phase Equilibria in Systems with an Esterification Reaction Using PC-SAFT

Simultaneous Predictions of Chemical and Phase Equilibria in Systems with an Esterification Reaction Using PC-SAFT

The Effect of Sulfate Electrolytes on the Liquid–Liquid Equilibrium of 2-MTHF/Water/5-HMF: Experimental Study and Thermodynamic Modeling

Influence of Solvents and Salts on CO₂ Solubility and the Impact on an Esterification Reaction

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Calculation of Multiphase Equilibria Containing Mixed Solvents and Mixed Electrolytes: General Formulation and Case Studies

Cited by 10 publications

References 86 publications

Simultaneous Predictions of Chemical and Phase Equilibria in Systems with an Esterification Reaction Using PC-SAFT

Simultaneous Predictions of Chemical and Phase Equilibria in Systems with an Esterification Reaction Using PC-SAFT

The Effect of Sulfate Electrolytes on the Liquid–Liquid Equilibrium of 2-MTHF/Water/5-HMF: Experimental Study and Thermodynamic Modeling

Influence of Solvents and Salts on CO2 Solubility and the Impact on an Esterification Reaction

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Influence of Solvents and Salts on CO₂ Solubility and the Impact on an Esterification Reaction