Mechanisms, Growth Rates, and Morphologies of Gas Hydrates of Carbon Dioxide, Methane, and Their Mixtures

Mechanisms of growth and dissociation, growth rates, and morphology of gas hydrates of methane, carbon dioxide, and two CH4:CO2 mixtures (80:20 and 30:70 nominal concentration) were studied using using high resolution images and very precise temperature control. Subcooling and a recently proposed mass transfer-based driving force were used to analyze the results. When crystal growth rates did not exceed 0.01 mm/s, all systems showed faceted, euhedral crystal habits at low driving forces. At higher driving forces and growth rates, morphologies were different for all systems. These results solve apparent contradictions in literature about the morphology of hydrates of methane, carbon dioxide, and their mixtures. Differences in the growth mechanism of methane-rich and carbon dioxide-rich hydrates were elucidated. It was also shown that hydrate growth of methane, carbon dioxide, and their mixtures proceed via partial dissociation of the growing crystal. Temperature gradients were used to dissociate hydrates at specific locations, which revealed a most interesting phenomenon: On dissociation, carbon dioxide-rich hydrates propagated onto the bare substrate while drawing water from the opposite side of the sample. Furthermore, it was shown that an abrupt change in morphology common to all systems could be correlated to a change in the slope of growth rate data. This change in morphology was explained by a shift in the crystal growth mechanism.