Thermal Regulation of Methane Hydrate Dissociation:Implications for Gas Production Models

摘要

Thermal self-regulation of methane hydrate dissociation at pressure,temperature conditions along phase boundaries,illustrated by experiment in this report,is a significant effect with potential relevance to gas production from gas hydrate.In surroundings maintained at temperatures above the ice melting point,the temperature in the vicinity of dissociating methane hydrate will decrease because heat flow is insufficient to balance the heat absorbed by the endothermic reaction:CH_4 centre dot nH_2O (s)=CH_4 (g)+nH_2O (1).Temperature decreases until either all of the hydrate dissociates or a phase boundary is reached.At pressures above the quadruple point,the temperature-limiting phase boundary is that of the dissociation reaction itself.At lower pressures,the minimum temperature is limited by the H_2O solid/liquid boundary.This change in the temperature-limiting phase boundary constrains the pressure,temperature conditions of the quadruple point for the CH_4-H_2O system to 2.55+-0.02 MPa and 272.85+-0.03 K.At pressures below the quadruple point,hydrate dissociation proceeds as the liquid H_2O produced by dissociation freezes.In the laboratory experiments,dissociation is not impeded by the formation of ice byproduct per se;instead rates are proportional to the heat flow from the surroundings.This is in contrast to the extremely slow dissociation rates observed when surrounding temperatures are below the H_2O solid/liquid boundary,where no liquid water is present.This "anomalous" or "self preservation behavior,most pronounced near 268 K,cannot be accessed when surrounding temperatures are above the H_2O solid/liquid boundary.