Hydrophobic Effect on Gas Hydrate Formation in the Presence of Additives

Additives such as surfactants, polymers, salts, and hydrophobic particles are well-known (and used) to influence gas hydrate formation (GHF). This paper reviews and discusses the mechanisms of their effects. The effects of additives on GHF appear to vary greatly from one additive to another. Even a given additive can change from a promoter to an inhibitor and vice versa when the working conditions are changed. The available literature cannot explain the diverse effects of additives. We argue that the hydrophobic effect plays a critical role in gas hydrate formation. A dissolved hydrophobe organizes the surrounding water into a clathrate-like structure and thereby promotes hydrate formation. A hydrophile, however, disrupts the surrounding water structure and inhibits hydrate formation. Moreover, cooperative hydrophobic interactions create an increased gas concentration around a hydrophobe, which also favors the hydrate formation. In contrast, a hydrophile competes with the gas for water and thereby hinders hydrate formation. In particular, when the additive is an amphiphile, the observed effect is the result of the competition between the hydrophobic moiety (a promoter) and hydrophilic moiety (an inhibitor). This hypothesis provides a universal explanation for the various effects of hydrate additives.