Jitendra Sangwai

Alkalis such as sodium hydroxide (NaOH) and calcium hydroxide [Ca(OH)2] find lots of applications in oil and gas industry where formation of methane hydrates (and resulting flow hindrance) is a common occurrence. While many hydrate inhibitors have been identified to maintain flow assurance, effects of these alkalis on the phase stability of methane hydrate have not yet been explored in detail. In this study, the phase behaviour of methane hydrate has been investigated in the presence of aqueous solutions of NaOH and Ca(OH)2 with varying concentrations of 0.005, 0.01, 0.02, and 0.04 mass fractions in a high pressure stirred tank reactor. The phase equilibrium of methane hydrate in aqueous alkali solutions has been generated in the pressure and temperature ranges of 4.27–7.90 MPa and 276.60–283.22 K, respectively. Both the alkalis have found to exhibit inhibition of methane hydrate formation, and the inhibition effect becomes more pronounced at higher concentrations of the alkalis, with NaOH performing as a better inhibitor than Ca(OH)2. A plausible mechanism for the same has also been discussed. The heat of dissociation has been calculated to show that the presence of the alkalis does not influence the structure (sI) of methane hydrate. In addition, a simple model based on the van der Waals-Platteeuw (vdW-P) thermodynamic model consisting of single parameter has been used to predict the phase equilibrium of methane hydrate in the presence of aqueous alkali solutions. The absolute average relative deviations (AARD%) in pressure for the model were measured for the 40 experimental data points generated in this work. The predictions are well within 4 % of the experimental values, which suggests that the model can adequately predict the methane hydrate phase stability in the presence of alkalis. These alkalis are used in various operations during exploration and production of oil and gas. This study therefore will assist in designing an effective and economic thermodynamic inhibitor for methane hydrate based on alkalis for the oil and gas industry.

Natural gas hydrate is a potential source of methane which needs to be extracted from under the sea bed. For the economic recovery of methane from natural gas hydrates, production approaches such as depressurization, thermal stimulation, and inhibitor injection are being investigated. However, studies involving hydrate-bearing clayey sediments and recovery of methane from such reservoirs are rare. This work investigates in detail the potency of hydrate dissociation methods such as depressurization by constant rate gas release, thermal stimulation and the combination of two for energy recovery from hydrate bearing clayey sediments underlying a free gas zone. Pure water and two different mud samples containing 3 and 5 wt% of bentonite were used for methane hydrate formation and dissociation studies. Thermodynamic study of methane hydrate in the presence of bentonite clay was also conducted for the above two concentrations. No considerable effect of clay on the inhibition or promotion of methane hydrate formation was observed. Initially, methane hydrate formation has been investigated using pure water, 3 and 5 wt% bentonite mud at an initial hydrate formation pressure of 8 MPa and at a temperature of 278.15 K. Subsequently, methane hydrate dissociation experiments were carried out using depressurization, thermal stimulation and their combination. The effect of the rate of gas release on hydrate dissociation by depressurization was investigated using two different rates of 10 mL/min and 20 mL/min. Thermal stimulation experiments were carried out for ΔT = 15 K at the rate of 7.5 K/hr and the results on methane recovery were recorded. The detailed investigation shows that the combination of the two methods is more efficient for methane production than the standalone method in clayey hydrate reservoir. This study provides important insights into the hydrate production methodology from clayey hydrate reservoirs.