A compositional kinetic model of hydrate crystallization and dissolution

Hydrates are crystallizing near and at the seafloor from gas vents on shelves where the sedimentation rate is high and hydrocarbons are being generated. When seafloor temperature, vent rate, or vent gas composition changes, these hydrates may become unstable and decompose. We have constructed a compositional kinetic model of hydrate crystallization and dissolution that can address these issues. The model crystallizes hydrate in compositional bins and allows each to dissolve at either a kinetically or compositionally controlled rate if vent gas composition or temperature causes it to become unstable. We empirically calibrate the model to venting at the Bush Hill hydrate mound in the offshore Louisiana Gulf of Mexico, show how variations in venting rate crystallize hydrate of diverse composition in the subsurface, and investigate how bottom water temperature variations similar to those measured could increase the rate of gas venting by destabilizing hydrates within a few meters of the seafloor. We show that increases in bottom water temperature can cause gas venting rates to increase similar to100%, as suggested by recent measurements, only if the dissolution kinetics are fast compared to the empirically calibrated crystallization kinetics and dissolution gases are removed rapidly enough that they do not thermodynamically inhibit the rate of dissolution. Model characteristics required to further investigate hydrate mound construction are identified.