Experimental and modeling study on the phase equilibria for hydrates of gas mixtures in TBAB solution

Accurate calculation of equilibrium formation conditions of hydrates is important for gas storage and separation based on hydrate technology. In this work, the hydrate formation conditions of a synthesized gas mixture in tetra-n-butyl ammonium bromide (TBAB) aqueous solution were measured at temperature ranging from 278.1 to 286.2 K. An inflection point in the P-T curve of hydrate phase equilibria was found. It is suggested that the hydrate structures transformed from semiclathrate hydrates to pure structure I hydrates with an increase in formation temperature. Then a thermodynamic model was proposed for calculating formation conditions of the semiclathrate hydrates formed from the gas mixtures+TBAB aqueous solution. The Patel-Teja equation of state was used to calculate the fugacity of gaseous hydrate former and several correlations were used to calculate the properties of TBAB. Ethylene molecules are supposed not to be able to occupy the dodecahedral small cages in the TBAB semiclathrate hydrates under the experimental P-T conditions. The presented model results show good agreement with the experimental data and the literature data.