Clathrate-hydrate film growth along water/hydrate-former phase boundaries—numerical heat-transfer study

This paper describes two analytic models for the heat-transfer-controlled lateral growth of a clathrate-hydrate film along a planar interface between liquid water and an immiscible hydrate-forming fluid (or guest fluid), such as methane or carbon dioxide. The two models are different from each other only regarding the assumption of the film-front geometry. Either model assumes the film to be uniform and constant in thickness, ignoring possible changes in the thickness on a time scale relevant to its lateral growth. Another fundamental assumption employed in the model is that the film's hydrate-forming front is maintained at the hydrate/guest/water three-phase equilibrium temperature, thereby forming a two-dimensional temperature distribution in the surrounding three-phase space. Based on these assumptions, the transient, two-dimensional conductive heat transfer from the film front into the three phases is formulated and numerically solved to give the instantaneous rate of lateral film growth (i.e., the linear speed of the film-front) along the water/guest-fluid interface, while the film thickness is arbitrarily assumed as a fitting parameter. By comparing the predicted rates of film growth with the corresponding experimental data obtained with methane or carbon dioxide as the guest fluid, we estimated the film thickness to be about 10–20 μm for the methane hydrate at a pressure of 9.06 MPa and about 0.5 μm for the carbon-dioxide hydrate at a pressure of 5 MPa.