Effects of Halogen Ions on Phase Equilibrium of Methane Hydrate in Porous Media

The influences of halogen ions extracted from sodium fluoride, sodium chloride, sodium bromide, and sodium iodide and their concentrations on methane hydrate phase equilibrium conditions in porous media were investigated experimentally using an orthogonal test method at a pressure of 8 MPa. The experimental results showed that the equilibrium temperature of methane hydrate decreased when halogen ions were added. The equilibrium temperature decreased with the increase of halogen ion concentrations. The influence of the sources of the halogens ion to the methane hydrate equilibrium temperature were insensitive according to variance analysis, which could be explained by about the same mean ionic activity coefficient (a dimensionless coefficient relates the activity to a measured concentration) of sodium fluoride, sodium chloride, sodium bromide, and sodium iodide. The experimental measurements were also in close agreement with the thermodynamic model of Song et al. (J. Nat. Gas Chem. 19, 241 (2010)), in which the mechanical equilibrium of force between the interfaces in a hydrate–liquid–vapor system was considered.