Premelting-Induced Agglomeration of Hydrates: Theoretical Analysis and Modeling

Resolving the long-standing problem of hydrate plugging in oil and gas pipelines has driven an intense quest for mechanisms behind the plug formation. However, existing theories of hydrate agglomeration have critical shortcomings, for example, they cannot describe nanometer-range capillary forces at hydrate surfaces that were recently observed by experiments. Here, we present a new model for hydrate agglomeration which includes premelting of hydrate surfaces. We treat the premelting layer on hydrate surfaces such as a thin liquid film on a substrate and propose a soft-sphere model of hydrate interactions. The new model describes the premelting-induced capillary force between a hydrate surface and a pipe wall or another hydrate. The calculated adhesive force between a hydrate sphere (R = 300 μm) and a solid surface varies from 0.3 mN on a hydrophilic surface (contact angle, θ = 0°) to 0.008 mN on a superhydrophobic surface (θ = 160°). The initial contact area is 4 orders of magnitude smaller than the cross-sectional area of the hydrate sphere and can expand with increasing contact time because of the consolidation of hydrate particles on the solid surface. Our model agrees with the available experimental results and can serve as a conceptual guidance for developing a chemical-free environmentally friendly method for prevention of hydrate plugs via surface coating of pipe surfaces.