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• 3D xenon hydrate shell meshes on water particle and ice sphere created from micro XCT. • Time-dependent hydrate shell thickness and inner/outer diameter were determined. • Novel 3D mesh method can quantify heterogeneous hydrate shell growth. Gas hydrates have gained increasing attention in energy and environmental fields and have potential applications in gas storage and transport, carbon dioxide sequestration, and flow assurance. Nevertheless, the kinetics of hydrate formation are still not well understood. In situ high-resolution X-ray computed tomography measurements were performed to monitor xenon hydrate formation on water droplets and ice spheres. For the first time, three-dimensional thickness meshes were used to quantify and visualize the kinetics of hydrate formation. The evolution of the hydrate morphology was investigated, and the time-dependent kinetic parameters were obtained, including the hydrate shell thickness and inner and outer diameters and the effective volume fraction of hydrate particles. The results indicate that the formation of gas hydrates undergoes an initial reaction-controlled stage followed by a mass-transfer-limited growth stage. For hydrate formation from a water droplet with an initial diameter of 1.66 mm, the hydrate shell thickness was approximately 30 μm and the effective volume fraction of hydrate particles was approximately 11% at 12 h after hydrate formation began. The standard deviation of the shell thickness, which indicates the surface roughness of the hydrate shell, increased with time for hydrate formation from water droplets. The results presented in this study renew our knowledge on the kinetics of hydrate formation, which is essential for their use in flow assurance and other hydrate-related technologies. [ABSTRACT FROM AUTHOR]

• 3D morphologies and time-dependent parameters of the hydrate shell are obtained. • Water is more mobile than gas in hydrates in the diffusion-controlled growth stage. • Protrusions growth on the outer surface of a hydrate shell is due to water permeation. • Effective diffusion coefficients of gas and water in hydrate are determined. Understanding the transport properties of water and guest molecules in dense hydrate structures is pivotal in controlling their formation and stability; this is nevertheless hindered by challenges in characterizing the time-varying diffusion and permeation process. This paper reports experimental results on the mass-transfer characteristics of water and guest molecules across hydrate shells during their formation from water droplets. The time-dependent 3D morphologies and parameters of hydrate shells were in-situ obtained via X-ray computed tomography to reveal the transport mechanism in hydrates. It was found that in the mass-transfer-limited stage, hydrate growth occurred primarily at the hydrate-gas interface, indicating a more mobile characteristic of water molecules in those hydrate shells than gas. The resulting outward permeation of water led to the growth of hydrate protrusions on the outer surface of the hydrate shell, suggesting a transition of the water transport schema through the hydrate shell from diffusion to permeation. Consequently, a diffusion-based shell growth model was developed to quantify the diffusivity of gas and water molecules in hydrates. Combining the measurements in the temperature range of 275.15–283.15 K, the effective diffusion coefficient of gas through the hydrates was estimated to be in the range of 1.34 × 10−14 − 1.90 × 10−13 m2/s, with that of interstitial water in the range of 2.87 × 10−12 − 3.83 × 10−11 m2/s. These results are of fundamental value in developing an improved understanding of the kinetics of hydrate formation from gas-water interfaces, which is essential in the optimization of hydrate-based techniques. [ABSTRACT FROM AUTHOR]