Applications of an Association Activity Coefficient Model, NRTL-PA, to Alcohol-Containing Mixtures

Bala, Aseel M.; Liu, Renming; Peereboom, Lars; Lira, Carl T.

doi:10.1021/acs.iecr.2c01415

Cited by 8 publications

(19 citation statements)

References 81 publications

(140 reference statements)

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“…Figure shows ternary LLE for a methanol–cyclohexane–hexane mixture, modeled again using NRTL-PA . Association parameters described earlier were also utilized for these mixtures, and the ternary LLE has been modeled reasonably well.…”

Section: Advantages Of Association Modelingmentioning

confidence: 81%

“…Hao and Chen have recently demonstrated a wide range of results with a similar combination of NRTL and TPT1 . The association options expressed in eqs – are becoming available in process simulators as the NRTL-PA model introduced in an accompanying manuscript in this special issue . NRTL-PA provides improved simultaneous representation of the phase equilibrium and excess enthalpy.…”

Section: Models In Current Engineering Practice and Association Theorymentioning

confidence: 99%

“…Activity coefficients are normalized for pure components (Lewis Randall framework) or at infinite dilution (Henry’s law framework) or are consistent with the fugacity of a pure component in the case of an equation of state model being utilized. While not an issue for association-theory-based equations of state, activity coefficient models based on association theory must properly express association relative to the pure component associated state. , …”

Section: Fundamental Requirements Of Mixture Phase Equilibrium Modelsmentioning

confidence: 99%

“…While possible, in principle, to determine them via the Gibbs–Duhem equation, uncertainties in measurements often lead to high uncertainties in the derived activity coefficient of the heavy component. Here association-based models have a distinct advantage over local composition models, since the association term with default adjustable binary parameters is the major contributor to activity coefficients …”

Section: Advantages Of Association Modelingmentioning

confidence: 99%

“…The figure includes some association constants regressed using only experimental mixture data and some regressed from pure component data only. Regression of pure component density and vapor pressure data is insufficient to clearly discriminate between the physical and chemical parameters that are both “sticky”. , Some mixture data are best included to regress the parameters especially if the systems include LLE . Pure component data provide insight using only temperature to vary density, whereas mixture data provide a wider range of density variation.…”

Section: Inferring Parameters For Association Modelsmentioning

confidence: 99%

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Wertheim’s Association Theory for Phase Equilibrium Modeling in Chemical Engineering Practice

Lira

Elliott

Gupta

et al. 2022

Ind. Eng. Chem. Res.

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Association and complex formation are the most important contributors to nonidealities in modeling phase equilibria. Models based on Wertheim's association theory are reviewed in the context of current industrial practice, showing great promise in resolving many of the shortcomings of the currently available models. Several pitfalls of common models are highlighted, showing the advantages of association theory. Infinite dilution activity coefficients can provide valuable insights into the liquid phase nonidealities. Trends for various mixture classifications are tabulated and explained simply in terms of "differences in molecular association". The need for a systematic procedure to characterize association parameters is cited as the most important barrier to broader implementation of these models. Improper characterizations can undermine the advantages of association theory, possibly confusing whether it offers any advantage. Resolving these issues will improve traditional small molecule phase equilibrium modeling and many other applications as well.

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Section: Advantages Of Association Modelingmentioning

confidence: 81%

Section: Models In Current Engineering Practice and Association Theorymentioning

confidence: 99%

Section: Fundamental Requirements Of Mixture Phase Equilibrium Modelsmentioning

confidence: 99%

Section: Advantages Of Association Modelingmentioning

confidence: 99%

Section: Inferring Parameters For Association Modelsmentioning

confidence: 99%

See 3 more Smart Citations

Wertheim’s Association Theory for Phase Equilibrium Modeling in Chemical Engineering Practice

Lira

Elliott

Gupta

et al. 2022

Ind. Eng. Chem. Res.

Self Cite

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Chemical Process Design and Simulation of the Production of Gamma‐Valerolactone: A Green Solvent for Halide Perovskites

Bisri,

Widharyanti,

Adhyaksa

2023

Energy Tech

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Enabling large‐scale perovskite photovoltaic production requires understanding the integrated chemical process flow of precursor ink. Herein, a chemical process design is proposed for producing halide perovskite ink using biomass‐derived gamma‐valerolactone (GVL) as a green solvent for the first time. The proposed design has a perovskite ink production capacity of 154 kg h−1 (at 1 m concentration), which is roughly equivalent to a peak power generation of 300 GW year−1 from perovskite modules. Process simulations in ASPEN Plus showed that the reactor temperature, feedstock flow rate, and precursor colloidal size greatly impact the final ink quality. Under optimum conditions, 98.4% purity of GVL can be achieved through a catalyzed reaction between levulinic acid and isopropyl alcohol with acetone (99.98%) and water (99.99%) as by‐products. Providing a realistic chemical reaction scheme for halide perovskite ink formation as well as understanding the changes in its chemical properties over time are paramount to further improving the proposed process.

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Beyond Flory–Huggins: Activity Coefficients from Perturbation Theory for Polar, Polarizable, and Associating Solvents to Polymers

Chapman

Fouad

2022

Ind. Eng. Chem. Res.

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We present a general relationship for the excess chemical potential that enables the development of activity coefficient models from free energy perturbation theory. We reveal the simple basis and approximations implicit in the Flory−Huggins theory and explain, apparently for the first time, the accuracy of the approach when there is a volume change on mixing. The result has implications in coarse-graining strategies for mesoscale modeling. Further, we present corrections for molecular size and shape as well as multiple association (hydrogen bonding) sites, multiple polar functional groups, and polarizability based on the statistical associating fluid theory (SAFT) equation of state and on the dipolar chain theory. The result is a general activity coefficient model with realistic molecular interactions. We present detailed equations for each chemical potential contribution in a SAFT activity coefficient model (SAFT-AC). Depending on the choice of mixing conditions, multiple terms can be made to cancel in the derivation and a simple activity coefficient model (SAFT-SAC) can be derived. Applications of SAFT-AC and SAFT-SAC are shown for mixtures containing polar, polarizable, and associating components. There are several advantages to the new approach to activity coefficient models. The model is applicable from solvents to polymers, each with multiple polar and hydrogen bonding functional groups. Each contribution from perturbation theory has been validated in comparison with molecular simulation results so that the accuracy of the model is known, and the model should extrapolate accurately beyond the range of fit. Further, the model is consistent with bulk equations of state, in this case, polar SAFT models, so that there is a smooth transition from the activity coefficient approach to the fugacity coefficient approach when necessary. The model derivation clearly defines approximations and conditions when the activity coefficient approach is valid so that a process simulation package can identify when to switch from an activity coefficient approach to a fugacity coefficient approach. Because of the direct connection to statistical mechanics-based theory, improvements of the activity coefficient model and extensions to other systems, including self-assembling systems, can be relatively straightforward. Since parameters in the model are the same as in SAFT models and related to models used in molecular simulations, this approach provides an opportunity to link workflows of activity coefficient models to equations of state and to molecular simulations and mesoscale models.

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Applications of an Association Activity Coefficient Model, NRTL-PA, to Alcohol-Containing Mixtures

Cited by 8 publications

References 81 publications

Wertheim’s Association Theory for Phase Equilibrium Modeling in Chemical Engineering Practice

Wertheim’s Association Theory for Phase Equilibrium Modeling in Chemical Engineering Practice

Chemical Process Design and Simulation of the Production of Gamma‐Valerolactone: A Green Solvent for Halide Perovskites

Beyond Flory–Huggins: Activity Coefficients from Perturbation Theory for Polar, Polarizable, and Associating Solvents to Polymers

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