Phase equilibria of methane and carbon dioxide clathrate hydrates in the presence of (methanol + MgCl2) and (ethylene glycol + MgCl 2) aqueous solutions
In this work, the experimental data for the equilibrium conditions of methane and carbon dioxide clathrate hydrates in the presence of (0.1 mass fraction methanol + 0.03, 0.1 mass fraction MgCl2) and (0.1, 0.2 mass fraction ethylene glycol + 0.1 mass fraction MgCl2) aqueous solutions at different temperature and pressure range 263.74 to 280.54 K and 0.98 to 8.02 MPa, respectively and for various concentrations of inhibitors are reported, which is not available in open literature. The equilibrium pressure-temperature curves were generated using an isochoric pressure-search method. The experimental results of methane and carbon dioxide clathrate hydrates in the presence of pure water and the above mentioned aqueous inhibitor solutions are compared with some selected experimental data from the literature in the presence of pure water, single glycol, alcohol or salt aqueous solutions to validate the experimental result and to show the inhibition effects of the aqueous solutions used in this work. The results show that the phase equilibrium of the quaternary system (H2O + ethylene glycol/methanol + CH 4/CO2 + MgCl2) is shifted to higher pressures/lower temperatures compared to the phase equilibrium of pure CH 4/CO2 due to the inhibition effect. Also, it has been observed that the quaternary system containing methanol has a more inhibition effect than the quaternary system containing ethylene glycol at the same mass fraction of the inhibitor in the aqueous solution. © 2013 Elsevier Ltd. All rights reserved.
Modeling of methane hydrate inhibition in the presence of green solvent for offshore oil and gas pipeline
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).
Effect of guest-dependent reference hydrate vapor pressure in thermodynamic modeling of gas hydrate phase equilibria, with various combinations of equations of state and activity coefficient models
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.
Thermodynamic modeling of phase equilibria of clathrate hydrates formed from CH4, CO2, C2H6, N2 and C3H8, with different equations of state
A thermodynamic model to predict three phase (L-H-V and I-H-V) equilibria of gas hydrates is presented. In this model we have employed a fugacity based approach where the hydrate phase is modeled using van der Waals-Platteeuw solid solution theory and the liquid phase activity coefficients are determined from the modified UNIFAC method. For the vapour phase fugacity calculations we have investigated three equations of state (EOS): Peng-Robinson-Stryjek-Vera (PRSV), Patel-Teja (PT) and Soave-Redlich-Kwong (SRK). This model employs only parameters reported in the literature. The coexistence pressures predicted by our model for the sI hydrates of methane, carbon dioxide and ethane are in reasonable agreement with experiments, whereas our model overestimates the coexistence pressures for the sII clathrates of nitrogen and propane. The predicted cage occupancies are found to increase with increasing temperature in the L-H-V equilibria. For I-H-V equilibria the cage occupancy is observed to decrease with temperature. We have also estimated the solubility of each guest in the liquid phase (for L-H-V equilibria) using the Henry's law. The solubilities predicted using all three EOS are in good agreement for all guest molecules, with the exception of nitrogen where at relatively higher temperatures the estimates from the PRSV EOS are noticeably lower than the corresponding predictions from the PT and SRK EOS.
Characterization and rheology of Krishna-Godavari basin sediments
The Krishna Godavari offshore basin to the east of India is a proven reserve, rich in natural gas hydrate. The impact of sediment characteristics on the hydrate formation has already been well established in open literature. In the present study, we have attempted to investigate the mineralogy of sediments collected from KG basin by elemental analysis (energy dispersive spectroscopy) and x-ray diffraction. Various physicochemical characteristics of the clayey sediments such as TDS, salinity, pH, conductivity and resistivity were analysed at various concentrations and compared together. Also, this paper highlights the rheological behavior of the sediment samples with concentrations of 20, 35 and 50 wt% at different experimental temperatures (278.15 K, 283.15 K and 288.15 K). Viscosity measurements were performed for a wide range of shear rates for all concentrations and comparative studies have been conducted on their exhibited behavior. The viscosity of sediment sample were found to be varying from 76.3 to 0.003 Pa s depending on the sediment concentration, temperature and shear rate. In addition, viscoelastic measurements were carried out at various angular frequencies for all the sediment samples. The work aims to characterise the sediments of KG basin and analyse the rheological behavior of sediment solution which has not yet been reported in open literature. This will provide vital information for possible methane recovery from KG basin hydrate reservoir by manipulating the host sediment behavior.
Phase equilibrium of semiclathrate hydrates of methane in aqueous solutions of tetra-n-butyl ammonium bromide (TBAB) and TBAB-NaCl
Phase equilibria of semiclathrate hydrates are important for their successful engineering applications due to more favorable process conditions compared to classical gas hydrate systems. Though sufficient information on the phase equilibria of semiclathrate hydrates of methane (CH4) in tetra-n-butyl ammonium bromide (TBAB) seems to be available, there are pronounced disagreements on the phase equilibrium data, particularly for 0.05 and 0.20 mass fraction (w) of TBAB. In this work, experimental studies are carried out to generate the equilibrium pressure (P) and temperature (T) for hydrates and semiclathrate hydrates of CH4 in an aqueous solution containing wTBAB=0.05 and 0.20 at P and T range of 1.02-13.73MPa and 281.63-294.54K, respectively. This study tries to clarify the discrepancy of published data in the literature and their reliability. Additionally, we present interesting insights into the phase behavior of semiclathrate hydrate of methane in TBAB based on the formation and dissociation curves observed in the experiments. It is observed that there existed two equilibrium points during the dissociation of semiclathrate hydrates of methane in TBAB; one closely corresponds to the pure methane hydrate phase stability curve and the second one to the semiclathrate hydrate system of methane. In addition phase equilibrium data is generated for the quaternary system of CH4+TBAB+H2O+NaCl for wNaCl=0.03 and 0.10 and wTBAB=0.05 and 0.20 in an aqueous solution at a P and T range of 1.65-20.71MPa and 281.19-296.38K, respectively. This is not yet available in the open literature. It is observed that NaCl inhibits the semiclathrate hydrate formation of CH4 in TBAB for wNaCl=0.03 and 0.10 in wTBAB=0.20 in the system. However, a promotion effect is observed for wNaCl=0.03 in wTBAB=0.05. This study calls for more detailed investigations on the effect of salts on semiclathrate hydrate systems, which may find potential use in engineering applications. © 2014 Elsevier B.V.
Prediction of phase stability conditions of gas hydrates of methane and carbon dioxide in porous media
With the growing need to explore non-conventional energy sources, the hydrates of natural gases offer a realistic solution in the need for alternative energy sources. Gas hydrates are typically entrapped in the porous media showing sensitive phase stability conditions. Models for phase stability for gas hydrate have not yet been extensively investigated for porous media and thus need attention. In this paper, the phase stability model is developed from the basic Chen and Guo model (Chem Eng J, 1998, 71:145) to accurately predict the phase behavior of the clathrate hydrates of CH4 and CO2 in porous media of varying pore sizes from 6nm to 100nm which mimics the naturally occurring porous environment. We also propose a new equation for calculating the activity of water in porous media as a function of the pore size, the wetting angle, the surface tension, and the shape factor of the pores for varied temperature conditions. The model results are validated against experimental data available in open literature and found satisfactory. The proposed model uses very few input parameters (data intrinsic) and thereby is very beneficial in predicting the stability of the hydrates in virgin gas reservoirs wherein the characteristics of the gas reservoir are largely unknown. The developed model may further be applied to the hydrate systems of other natural gases in porous medium with suitable modifications. © 2014 Elsevier B.V.
Effects of sodium hydroxide and calcium hydroxide on the phase equilibria of methane hydrates
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.
A robust model for the phase stability of clathrate hydrate of methane in an aqueous systems of TBAB, TBAB + NaCl and THF suitable for storage and transportation of natural gas
Semiclathrate hydrates of natural gas have shown potential applications in natural gas storage and transportation. Promoters, viz., tetra-n-alkyl ammonium bromide (TBAB) and tetrahydrofuran (THF) have positive impacts on the phase stability condition in lowering the required pressure for hydrate formation. As part of this work, a predictive model for the phase stability of gas hydrate, which are necessary to understand the phase behavior of methane (CH4) hydrate in promoters, has been proposed. The fugacity of hydrate former in the gaseous phase is calculated from Peng-Peng-Robinson equation of state (PR-EoS), while the fugacity of water in the liquid phase is computed from recently proposed Pitzer-Mayorga-Zavitsas-Hydration (PMZH) model for TBAB system and non-random two liquid (NRTL) model for THF system. The van der Waals Plattew model is employed for the hydrate phase. The vapor pressure of water in the empty hydrate lattice as well as Langmuir adsorption constants have been expressed in terms of concentration of the promoters. The predictions of the proposed model are found to be match well with experimental data on phase stability of CH4 hydrate formed using TBAB and THF aqueous systems. Furthermore, the developed model is employed for the prediction of phase stability conditions of the semiclathrate hydrates of CH4 in TBAB + NaCl system. The developed model is found to interpret the promotion effects of both TBAB (with or without NaCl) and THF on phase stability conditions of CH4 hydrate. AARD-P% with PMZH model are observed to be 3.21% and 8.73% for semiclathrate hydrates of CH4 in TBAB and TBAB + NaCl, respectively, and 8.56% for clathrate hydrate of CH4 in THF. The model may be extended to evaluate the phase stability conditions of hydrates of multicomponent gas systems in TBAB/THF which are necessary for real field applications.
An improved model for the phase equilibrium of methane hydrate inhibition in the presence of ionic liquids
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.