Natural gas containing trace amounts of water is frequently
liquefied
at conditions where aqueous solids are thermodynamically stable. However,
no data are available to describe the kinetics of aqueous solid formation
at these conditions. Here, we present experimental measurements of
both solid formation kinetics and solid–fluid equilibrium for
trace concentrations of (12 ± 0.7) ppm water in methane using
a stirred, high-pressure apparatus and visual microscopy. Along isochoric
pathways with cooling rates around 1 K·min–1, micron-scale aqueous solids were observed to form at subcoolings
of (0.3–8.6) K, relative to an average equilibrium melting
temperature of (253 ± 1.9) K at (8.9 ± 0.08) MPa; these
data are consistent with predicted methane hydrate dissociation conditions
within the uncertainty of both the experiment and model. The 36 measured
formation events were used to construct a cumulative formation probability
distribution, which was then fitted with a model from Classical Nucleation
Theory, enabling the extraction of kinetic and thermodynamic nucleation
parameters. While the resulting nucleation parameter values were comparable
to those published for methane hydrate formation in bulk-water systems,
the observed growth kinetics were distinctly different with only a
small percentage of the water in the system converting into micron-scale
solids over the experimental time scale. These results may help explain
how cryogenic heat exchangers in liquefied natural gas facilities
can operate for long periods without blockages forming despite being
at very high subcoolings for aqueous solids.
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