Predicting CO2 solubility in aqueous and organic electrolyte solutions with ePC-SAFT advanced

Schick, Daniel; Bierhaus, Lena; Strangmann, Alexander; Figiel, Paul; Sadowski, Gabriele; Held, Christoph

doi:10.1016/j.fluid.2022.113714

Cited by 14 publications

(15 citation statements)

References 95 publications

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“…Reactive processes may offer several advantages over their non-reactive counterparts, such as an increase in reaction yield and selectivity, the overcoming of thermodynamic restrictions (e.g., azeotropes), energy saving or capital cost reduction [ 17 , 18 , 19 ]. Further, reactions in multiple phases systems are encountered in living systems such as coacervates [ 20 , 21 ], in downstream processes for biomolecules’ purification [ 22 , 23 ] or in geological fluid systems [ 24 ]. In process engineering, several methods have been developed so far to generate feasible flowsheets for a given separation/reaction task or to dimension and optimize the required unit operations [ 17 ], with all the proposed methods relying on the availability of experimental data.…”

Section: Introductionmentioning

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: Introductionmentioning

confidence: 99%

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

2023

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“…A similar effect on CO 2 solubility has also been reported by Pabsch et al for other electrolytes, so that it is likely that other bases show a similarly adverse effect on the CO 2 solubility. [21] Overall, the calculations reveal that CO 2 is the limiting component in the carboxylation. Thus, the reaction solution is strongly basic, which explains why even a CÀ H deprotonation of acetylene is possible.…”

Section: Introductionmentioning

confidence: 86%

Carboxylation of Acetylene without Salt Waste: Green Synthesis of C₄ Chemicals Enabled by a CO₂‐Pressure Induced Acidity Switch

et al. 2023

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The inherent formation of salt waste in C−H carboxylations is a key obstacle precluding the utilization of CO2 as C1 building block in the industrial synthesis of base chemicals. This challenge is addressed in a circular process for the production of the C4 base chemical dimethyl succinate from CO2 and acetylene. At moderate CO2 pressures, acetylene is doubly carboxylated in the presence of cesium carbonate. Hydrogenation of the C−C triple bond stabilizes the product against decarboxylation. By increasing the CO2 pressure to 70 bar, the medium is reversibly acidified, allowing an esterification of the succinate salt with methanol. The cesium base and the hydrogenation catalyst are regenerated and can be reused. This provides the proof of concept for a salt‐free route to C4 chemicals from biogas (CH4/CO2). The origin of this reversible acidity switch and the critical roles of the cesium base and the NMP/MeOH solvents were elucidated by thermodynamic modeling.

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“…The phase transition in the systems was monitored through two sapphire windows (front and back). For a detailed description of the experimental apparatus, please refer to Vogelpohl et al 35 and Schick et al 13 Before pressurizing the HPVVV, a predefined composition of aqueous or organic electrolyte solutions was added to the cell, and the temperature was set to the desired experimental condition. Next, supercritical CO 2 (p = 250 bar and T = 308.15 K) was pumped into the HPVVV using a syringe pump (260D, ISCO, Lincoln, USA).…”

Section: Experimental Methods 321 Measuring Co 2 Solubility In Solven...mentioning

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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Predicting CO2 solubility in aqueous and organic electrolyte solutions with ePC-SAFT advanced

Cited by 14 publications

References 95 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

Carboxylation of Acetylene without Salt Waste: Green Synthesis of C₄ Chemicals Enabled by a CO₂‐Pressure Induced Acidity Switch

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

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Predicting CO2 solubility in aqueous and organic electrolyte solutions with ePC-SAFT advanced

Cited by 14 publications

References 95 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

Carboxylation of Acetylene without Salt Waste: Green Synthesis of C4 Chemicals Enabled by a CO2‐Pressure Induced Acidity Switch

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

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Carboxylation of Acetylene without Salt Waste: Green Synthesis of C₄ Chemicals Enabled by a CO₂‐Pressure Induced Acidity Switch

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