Technical Notes - Metastable Equilibrium in the Dew Point Determination of Natural Gases in the Hydrate Region

The dew point of natural gas which has been in equilibrium with gas hydrates has been reported to be lower than that obtained for natural gas in equilibrium with water1,? Hammerschmidt' reports a lowering of the dew point of 13 F for a natural gas in equilibrium with hydrate at 380 F and 525 psi. Records and Seely2 likewise show that the dew point of gas leaving hydrate separators' is as much as 150 F below the separator temperature. This paper presents the reasons for the observed differences between the equilibrium temperatures and the dew point temperatures. Descriptions of the dew point determination by the Bureau of Mines and ASTM tester3 indicate that the dew point is taken as the temperature at which liquid water droplets first begin to appear on the cooled mirror surface even though the temperatures involved are below that required for the formation of gas hydrates or ice. PRESSURE-TEMPERATURE DIAGRAM FOR METHANE-WATEK SYSTEM Fig. 1 presents a schematic pressure-temperature diagram for the methane-water system" for some constant pressure between the critical pressures of pure methane and pure water i.e., pressures frequently encountered in pipeline operations. The possible equilibrium relations are shown by the heavy solid lines. Curve AE represents the saturated water content or dew point of gas in equilibrium with a water-rich liquid solution while curve EF represents the dew point of gas in equilibrium with hydrates. In addition the dotted line DE labelled "metastable dew point" is introduced to explain the apparent discrepancy betwceen the dew point determination and gas-hydrate equilibria. Thermodynamics place certain restrictions on the location of line DE6, namely, that (1) the concentration of water along the line DE be greater than the concentration of water along EF or that the metastable line split the angle formed by the intersection of line GE and EF