Phase equilibrium measurements for clathrate hydrates of flue gas (CO2 + N2 + O2) in the presence of tetra-n-butyl ammonium bromide or tri-n-butylphosphine oxide

• Semi-clathrate hydrate phase equilibria for ternary gas mixture of CO2, N2, and O2 are reported.
• An isochoric pressure-search method was used.
• TBPO outperforms TBAB in promoting the formation of flue gas hydrate.

This paper reports the measured hydrate phase equilibria of simulated flue gas (12.6 vol% CO2, 80.5 vol% N2, 6.9 vol% O2) in the presence of tetra-n-butyl ammonium bromide (TBAB) or tri-n-butylphosphine oxide (TBPO), at (0, 5 and 26) wt%, respectively. The measurements of the phase boundary between (hydrate + liquid + vapor) (H + L + V) phases and (liquid + vapor) (L + V) phases were performed within the temperature range (275.97 to 293.99) K and pressure range (1.56 to 18.78) MPa with using the isochoric step-heating pressure search method. It was found that addition of TBAB or TBPO allowed the incipient equilibrium hydrate formation conditions for the flue gas to become milder. Compared to TBAB, TBPO was largely more effective in reducing the phase equilibrium pressure.