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Solid-phase CO2 commonly known as dry ice, can pose a serious risk in numerous chemical
processes, including carbon capture, transport and storage (CCS), Liquefied Natural Gas (LNG)
applications, and cryogenic biogas upgrading. If temperature or pressure drops sufficiently, solid CO2 can form and block critical equipment such as vent lines or safety relief systems. A dislodged CO2 crystal traveling at high velocity can also damage equipment and endanger personnel [1].
Solidification of CO2 can be predicted by combining equations of state (EoS) for the fluid and
solid phases with a phase-equilibrium algorithm. In this work, we assessed a range of model
combinations. The most significant difference in the accuracy of the fluid-solid phase equilibrium
predictions was due to the choice of fluid EoS. Here, we evaluated three cubic, two multiparameter
and three EoS based on statistical associating fluid theory (SAFT).
The evaluation covered a wide range of mixtures and operating conditions. For CCS-relevant
mixtures, the simple cubic Peng-Robinson (PR) gave the lowest overall Mean Absolute Percentage
Deviation (MAPD) of 1.4% in the solidification temperature. For LNG applications, the multiparameter
EoS-CG [2] was the most accurate, yielding a MAPD below 1%. Among the SAFT-type models,
PCP-SAFT [3] performed best, underscoring the importance of explicitly accounting for the
quadrupole moment of CO2 in the description.
Because the standard PR gave a better agreement with experimental data than translated consistent PR (tc-PR) [4], the α-function of tc-PR was refitted by using vapour-pressure data of pure
CO2 below the triple point. This improved the MAPD for solid-liquid equilibria in mixtures from 2.4%
(original) to 1.6% (refitted), even though only pure-CO2 data were used in the regression. If a reliable
solid-phase EoS is available, the inclusion of solid–fluid equilibrium data in the EoS regression offers
a promising route to improving the pure-fluid formulation and, consequently, the prediction of
solidification and solubility limits in mixtures.
Significant references:
1. M. Vitali, F. Corvaro, B. Marchetti, and A. Terenzi. International Journal of Greenhouse Gas Control
2022, 114, 103605.
2. T. Neumann, S. Herrig, I.H. Bell, R. Beckmüller, E.W. Lemmon, M. Thol, and R. Span. International
Journal of Thermophysics 2023, 44, 178
3. J. Gross, and J. Vrabec. AIChE Journal 2006, 52, 1194–1204.
4. Y. Le Guennec, S. Lasala, R. Privat, and J.-N. Jaubert. Fluid Phase Equilibria, 2016, 427, 513–
538.