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

• A novel model for methane hydrate in TBAB and THF has been developed.
• Pitzer-Zavitsas hydration model used for fugacity of the water in liquid phase.
• Phase stability of CH4 hydrate in TBAB, TBAB + NaCl and THF are investigated.
• Model provides the effect of promoters on CH4 hydrate formation.
• This model shows satisfactory results with literature data.

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.