HYDRATE NUCLEATION MEASUREMENTS USING HIGH PRESSURE DIFFERENTIAL SCANNING CALORIMETRY Hester, Keith C.; Davies, Simon R.; Lachance, Jason W.; Sloan, E. Dendy; Koh, Carolyn A.
Understanding when hydrates will nucleate has notable importance in the area of flow assurance. Attempts to model hydrate formation in subsea pipelines currently requires an arbitrary assignment of a nucleation subcooling. Previous studies showed that sII hydrate containing a model water-soluble former, tetrahydrofuran, would nucleate over a narrow temperature range of a few degrees with constant cooling. It is desirable to know if gas phase hydrate formers, which are typically more hydrophobic and hence have a very low solubility in water, also exhibit this nucleation behavior. In this study, differential scanning calorimetry has been applied to determine the hydrate nucleation point for gas phase hydrate formers. Constant cooling ramps and isothermal approaches were combined to explore the probability of hydrate nucleation. In the temperature ramping experiments, methane and xenon were used at various pressures and cooling rates. In both systems, hydrate nucleation occurred over a narrow temperature range (2-3°C). Using methane at lower pressures, ice nucleated before hydrate; whereas at higher pressures, hydrate formed first. A subcooling driving force of around 30°C was necessary for hydrate nucleation from both guest molecules. The cooling rates (0.5-3°C/min) did not show any statistically significant effect on the nucleation temperature for a given pressure. The isothermal method was used for a methane system with pure water and a water-in-West African crude emulsion. Two isotherms (-5 and -10°C) were used to determine nucleation time. In both systems, the time required for nucleation decreased with increased subcooling.
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