Hydrate—A Mysterious Phase or Just Misunderstood?

Abstract

Hydrates that form during transport of hydrocarbons containing free water, or water dissolved in hydrocarbons, are generally not in thermodynamic equilibrium and depend on the concentration of all components in all phases. Temperature and pressure are normally the only variables used in hydrate analysis, even though hydrates will dissolve by contact with pure water and water which is under saturated with hydrate formers. Mineral surfaces (for example rust) play dual roles as hydrate inhibitors and hydrate nucleation sites. What appears to be mysterious, and often random, is actually the effects of hydrate non-equilibrium and competing hydrate formation and dissociation phase transitions. There is a need to move forward towards a more complete non-equilibrium way to approach hydrates in industrial settings. Similar challenges are related to natural gas hydrates in sediments. Hydrates dissociates worldwide due to seawater that leaks into hydrate filled sediments. Many of the global resources of methane hydrate reside in a stationary situation of hydrate dissociation from incoming water and formation of new hydrate from incoming hydrate formers from below. Understanding the dynamic situation of a real hydrate reservoir is critical for understanding the distribution characteristics of hydrates in the sediments. This knowledge is also critical for designing efficient hydrate production strategies. In order to facilitate the needed analysis we propose the use of residual thermodynamics for all phases, including all hydrate phases, so as to be able to analyze real stability limits and needed heat supply for hydrate production.