Experimental data on phase behavior of simple tetrabutylphosphonium bromide (TBPB) and mixed CO₂ + TBPB semiclathrate hydrates

The phase behavior of simple and mixed semiclathrate hydrates formed from CO₂ + tetrabutylphosphonium bromide (TBPB) + water mixtures was investigated by pressure-controlled differential scanning calorimetry (DSC) at TBPB concentrations in the range of 0 to 0.073 mole fraction and at CO ₂ pressure in the range of (0 to 2.0) MPa. In a previous article we demonstrated that TBPB + CO₂ mixed hydrates present high dissociation enthalpies and could be used as phase change material, covering the range of temperature from (284.6 to 289.0) K, for secondary refrigeration applications. The present work investigates a broader domain of compositions, resulting in x-T phase diagrams at atmospheric conditions and at various CO₂ pressures. These data are required to model the potential latent heat of hydrate slurries as a function of gas pressure and aqueous phase composition over the whole range of interest for refrigeration purposes. The results presented show that adding TBPB to the water at low concentration (0.0058 mole fraction) decreases the pressure of formation of CO₂ hydrates to 0.5 MPa at 281.6 K, instead of 3.5 MPa at the same temperature in the absence of a promoter. Crystallization of CO₂ + TBPB hydrate could therefore offer an attractive means of capture for CO₂.