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Vapor-liquid equilibrium (VLE) is a family of first-principled thermodynamic models for transcritical multiphase flows, which can accurately capture the phase transitions at high-pressure conditions that are difficult to deal with using other models. However, VLE-based computational fluid dynamics (CFD) simulation is computationally very expensive for multi-component systems, which severely limits its applications to real-world systems. In this work, we developed a new ISAT-VLE method based on the in situ adaptive tabulation (ISAT) method to improve the computational efficiency of VLE-based CFD simulation with reduced memory usage. We developed several ISAT-VLE solvers for both fully conservative (FC) and double flux (DF) schemes. New methods are proposed to delete redundant records in the ISAT-VLE table and the ISAT-VLE method performance is further improved. To improve the convergence of the VLE solvers, a modified initial guess for equilibrium constant is also introduced. Simulations of high-pressure transcritical two-phase temporal mixing layers and shock-droplet interaction were conducted using the ISAT-VLE CFD solvers. The simulation results show that the new method obtains a speed-up factor approximately from 10 to 60 and the ISAT errors can be controlled within 1%. The shock-droplet interaction results show that the DF scheme can achieve a higher speed-up factor than the FC scheme. The two sets of simulations exhibit the phase separation at high-pressure conditions. It was found that even at supercritical pressures with respect to each component, the droplet surface could still be in a subcritical two-phase state, because the mixture critical pressure is often significantly higher than each component and hence triggers phase separation. In addition, a shock wave could partially or completely convert the droplet surface from a subcritical two-phase state to a single-phase state by raising temperature and pressure.
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Assessing the Quality of Molecular Simulations for Vapor−Liquid Equilibria: An Analysis of the TraPPE Database
As molecular modeling and simulation techniques become increasingly important sources of thermophysical property and phase equilibrium data, the ability to assess the robustness of that data becomes more critical. Recently, the use of the compressibility factor (Z) has been suggested as a metric for testing the quality of simulation data for vapor−liquid equilibria (VLE). Here, we analyze predicted VLE data from the transferable potentials for phase equilibria (TraPPE) database and show that, apart from data entry or typographical errors, Z will always be well-behaved in Gibbs ensemble Monte Carlo (GEMC) simulations even when the simulations are not sufficiently equilibrated. However, this is not true for grand canonical Monte Carlo simulations. When the pressure is calculated from the internal forces, then pressure and density are strongly correlated for the vapor phase and, for GEMC simulations, it is recommended to treat Z as an instantaneous mechanical property. From analysis of the TraPPE VLE data, we propose a complementary metric based on the predicted vapor pressures at three neighboring temperatures and their deviation from a local Clausius−Clapeyron fit.
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- Award ID(s):
- 1835067
- PAR ID:
- 10193270
- Date Published:
- Journal Name:
- Journal of chemical and engineering data
- Volume:
- 65
- Issue:
- 3
- ISSN:
- 0021-9568
- Page Range / eLocation ID:
- 1330 - 1344
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.jced.9b00756
