LAUSR

Clathrate hydrates can spontaneously form under typical conditions found in oil and gas pipelines. The agglomeration of clathrates into large solid masses plugs the pipelines, posing adverse safety, economic, and environmental threats. Surfactants are customarily used to prevent the aggregation of clathrate particles and their coalescence with water droplets. It is generally assumed that a large contact angle between the surfactant-covered clathrate and water is a key predictor of the antiagglomerant performance of the surfactant. Here we use molecular dynamic simulations to investigate the structure and dynamics of surfactant films at the clathrate–oil interface, and their impact on the contact angle and coalescence between water droplets and hydrate particles. In agreement with the experiments, the simulations predict that surfactant-covered clathrate–oil interfaces are oil wet but super-hydrophobic to water. Although the water contact angle determines the driving force for coalescence, we find that a large contact angle is not sufficient to predict good antiagglomerant performance of a surfactant. We conclude that the length of the surfactant molecules, the density of the interfacial film, and the strength of binding of its molecules to the clathrate surface are the main factors in preventing the coalescence and agglomeration of clathrate particles with water droplets in oil. Our analysis provides a molecular foundation to guide the molecular design of effective clathrate antiagglomerants.