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.

In offshore gas transmission pipeline systems, typically gas and water are produced under high pressure and low temperature conditions causing the formation of gas hydrates blocking pipelines. Thermodynamic modeling is necessary to understand the phase stability of hydrate in the presence of green solvents namely, ionic liquids (ILs). In this work, the thermodynamic models are based on the computation of fugacity of hydrate phase using Van der Waals and Platteeuw solid solution theory combined with Peng - Robinson equation of state (PR-EoS) for fugacity of hydrate former in the gas phase and the computation of fugacity of aqueous water phase using activity coefficient models such as the non - random two - liquid (NRTL) model and Pitzer - Mayorga model. The model results are compared with available experimental data from open literature and observed to be in good agreement with the reported literature. Finally, the hydrate suppression temperature due to ILs on methane hydrate is calculated to know the inhibition effectiveness of IL on methane hydrate formation in offshore pipeline system. The overall accuracy of Pitzer-Mayorga model is found to be 5.8 % while NRTL model's accuracy was 6.3 % for various ILs and methane hydrate system. Model results further indicated that ILs with shorter alkyl chain length exhibit better inhibition effect. The model developed in this work shows potential application in the determination of hydrate phase stability using green solvent for offshore oil field applications. Copyright © 2014 by the International Society of Offshore and Polar Engineers (ISOPE).

In this work, a thermodynamic model is developed and used to predict the phase stability conditions for methane hydrate-ionic liquid (IL)-water system. The hydrate phase is computed from modified van der Waals-Platteeuw model. The Peng-Robinson equation of state (PR-EoS) and developed activity model as a combination of Pitzer-Mayorga-Zavitsas-hydration model is used to evaluate the fugacities of gas and liquid phases, respectively. The hydrate phase stability prediction is also computed using the liquid phase activity predicted by NRTL and Pitzer-Mayogra models, separately, and is compared with the results predicted from the developed model. The model predictions are compared with experimental results on the phase stability of methane hydrate reported in open literatures for 21 ILs. The 21 ILs chosen from various ionic groups such as tetraalkylammonium, pyrrolidinium, imidazolium cationic family with various anion group such as halides (Cl, Br, I), sulphate (HSO4, ethylsulphate), tetrafluoroborate (BF4) and dicyanamide (DCA). The absolute average relative deviation in predicted pressure (AARD-P) with developed Pitzer-Mayorga-Zavitsas-hydration-model is improved to 1.60% and non-random two liquid (NRTL), Pitzer-Mayorga model showed 2.02% and 1.77% with 120 data points in the temperature range of 272.1-291.59K and pressure range of 2.48-20.67MPa. For 120 data points of phase stability conditions of 21 ILs, 39.2% of the predicted equilibrium pressures (47 data points) were within relative absolute deviation of 0.0-1.0%, 29.2% of the equilibrium pressures (35 data points) were within absolute deviation of 1.01-2.5%, 25.8% of data (31 data points) were within 2.51-7.5% which are mainly for data with low concentrations of ILs and only 5.8% of data (7 data points) showed relative absolute deviations above 7.5% which are observed mainly for data with high concentrations of ILs. Further, the model is used to calculate the inhibition effect of selected 21 ILs on methane hydrate formation.