Characterization of Gas Hydrates Formation and Dissociation Using Thermal Analysis and Calorimetry

Abstract:

In general, the gas hydrates are formed at low temperature and high pressure which requires a special technique to mimic the natural conditions. The hydrate thermal properties: heat capacity, heat of dissociation, are crucial for evaluating the effects on climate change and for a prediction of the gas production rates from hydrate reservoirs. The effect of the porous materials on the dissociation of synthetic methane hydrates was investigated at 150 – 300 K and atmospheric pressure. Another experiment with methane hydrates, but at high pressure (20 MPa) was performed at near room temperature using a highly sensitive micro-differential scanning calorimeter with a specifically design high pressure vessel (the vessel can withstand a pressure up to 1000 bars). The thermal cycle for measuring the methane hydrate dissociation in water includes cooling down a water solution under a certain methane pressure (30 to 350 bars) to -30 C to allow water crystallization and hydrate formation, then heated up to room temperature. The endothermic peak, following the ice melting is associated to the hydrate dissociation process and gives the enthalpy of the hydrate decomposition. The kinetics of the hydrates formation could also be predicted by a rapid DSC cooling experiment followed by isothermal step and heating. Both dissociation and specific heats of synthetic methane and ethane hydrates were measured under high-pressure condition by using a heat-flow type calorimeter to understand thermodynamic properties of gas hydrates under submarine/sublacustrine environments. The large reserves of natural gas are present as clathrate hydrates in permafrost regions and beneath the oceans have generated interest in the study of their thermophysical properties such as heat capacity and thermal conductivity. The effect of isotopic substitution in both THF and water on the eutectic and hydrate melting temperatures in water-tetrahydrofuran systems studied by DSC will be shown as an example.