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.

Using the van der Waals solid solution theory and the fugacity-based approach of Klauda and Sandler, a thermodynamic model to predict the phase equilibria of gas hydrates using an Equation of State (EOS) and an Activity Coefficient Model (ACM) is presented. Here, we have studied five EOS models, that are, Peng-Robinson-Stryjek-Vera (PRSV), Patel-Teja (PT), Soave-Redlich-Kwong (SRK), Peng-Robinson (PR), and Redlich-Kwong (RK) to calculate the gas phase fugacity and four ACMs, that are, modified UNIFAC (mUNIFAC), UNIQUAC, Wilson and NRTL to model the liquid phase non-ideality. The Wilson and NRTL activity coefficient models have previously been used for systems containing additional chemicals in the liquid phase but not for pure water in coexistence with gas hydrates, to the best of our knowledge, and this has been explored in this work. By making the empty hydrate vapor pressure parameters guest dependent, the model improves upon the predictions from our previous model for sI and sII hydrates significantly and has drastically reduced the errors especially in modeling sII hydrates. The best combinations of EOS and ACM in L-H-V equilibrium and best EOS for I-H-V equilibrium, respectively, for each compound, to be used in the guest dependent model from the 100 combinations of EOS and ACM (for L-H-V equilibrium) and 25 possible EOS options (for I-H-V equilibrium) examined are: RK–mUNIFAC and SRK for CH4, RK–mUNIFAC and PRSV for CO2, RK–mUNIFAC and PR for C2H6, SRK–mUNIFAC and SRK for N2, and PR–NRTL and RK for C3H8. While different EOS work well for CH4, CO2, C2H6 and C3H8 hydrates in L-H-V and I-H-V equilibria, the SRK EOS works well for N2 hydrates in both L-H-V and I-H-V equilibria. We have also reported the solubilities of guest species in liquid water in equilibrium with hydrates and the hydrate cage occupancies from the models producing the least error as data on these facets is limited.

Enhanced kinetics of carbon dioxide (CO2) hydrate formation will assist in developing technologies for CO2 gas storage, carbon capture and sequestration (CCS), and potentially for methane production from natural gas hydrates. The present work is focused on understanding the kinetics of CO2 hydrate formation in both bulk and porous media with pure water and seawater under the influence of non-toxic and low-cost inorganic emulsifiers or builders. Sodium tripolyphosphate (STPP) and tetrasodium pyrophosphate (TSPP) was used in a very low concentration of 0.2 wt.% to promote its economic viability. The experiments were carried out in a 300 mL stirred tank reactor and 100 mL porous bed reactor with an initial pressure of 3.5 MPa and 274.65 K with pure water and seawater, respectively. The porous bed was made with 0.15 mm silica sand with 70% water saturation. Both STPP and TSPP showed significant improvement in induction time for CO2 hydrate formation. Moreover, STPP showed reasonable enhancement in CO2 gas uptake compared to TSPP in both bulk and porous bed with both pure water and seawater. The average rate of hydrate formation was also better for STPP with multiple growth peaks. The results obtained will enhance hydrate-based technologies for efficient CO2 sequestration in shallow subsea sediments.