Semi-clathrate hydrate phase stability conditions for methane + TetraButylAmmonium Bromide (TBAB)/TetraButylAmmonium Acetate (TBAA) + water system: Experimental measurements and thermodynamic modeling

Abstract

One of the promising applications of clathrate/gas hydrates is the transport and storage of natural gas. Semi-clathrate hydrates have received more attention due to milder pressure/temperature stability conditions compared to ordinary clathrate hydrates. The most commonly reported semi-clathrate hydrates are formed from a combination of gas + water + quaternary ammonium salts. In this work, a total of 53 equilibrium data for semi-clathrate hydrates of methane + TetraButylAmmonium Bromide (TBAB)/TetraButylAmmonium Acetate (TBAA) aqueous solutions were experimentally measured. For TBAB, three concentrations including 0.0350, 0.0490, and 0.1500 mass fractions were used. For TBAA, a solution with a 0.0990 mass fraction was used. Additionally, the modified Chen–Guo model was applied to calculate the hydrate phase equilibrium conditions of methane + TBAB/TBAA aqueous solutions. The model can accurately calculate the aforementioned semi-clathrate hydrate phase equilibrium conditions with the Average Absolute Deviations ((AAD)T and (AAD)P) of 0.1 K and 0.08 MPa, respectively. The temperature increments for 0.0350, 0.0490, and 0.1500 mass fractions of TBAB are 7.7, 9.4, and 13.5 K, respectively. This value for 0.0990 mass fraction of TBAA is 6.2 K. Therefore, it is concluded that TBAB is a stronger hydrate promoter compared to TBAA.