Formation kinetics of the mixed cyclopentane-carbon dioxide hydrates in aqueous sodium chloride solutions

Abstract

Hydrate formation from cyclopentane (CP) and carbon dioxide was measured at 281 K by powder X-ray diffraction (PXRD) and macroscopic methods. The effect of initial pressure and CP mass fraction in liquid phase was analyzed. The results showed that hydrate formation was assumed to start with the nucleation of the mixed CP-CO2 hydrate with small fraction of CO2 followed by a large continuous CO2 adsorption. Initial pressure was found to have a positive correlation with the total CO2 consumptions when the initial pressure was below 2.5 MPa. However, the total CO2 consumptions dropped by over a half as the initial pressure was 3.0 MPa. PXRD revealed that all the hydrate samples formed at different initial pressures were structure II. The CO2 consumptions were assumed to be inhibited by the competitive occupation of 51264 cages between CP and CO2 molecules when the initial pressure was above 2.5 MPa. The CO2 consumptions were also found to be reduced as the CP mass fraction was above 0.25. An excess of CP molecules was not assumed to strengthen the formation of the mixed CP-CO2 hydrates at the initial stage, but increased the thickness of liquid CP film at aqueous brine and hydrate particles, which increased the diffusion resistance of CO2 molecules. Therefore, the suitable initial pressure and the CP mass fraction for the mixed CP-CO2 hydrate formation should be around 2.5 MPa and 0.2, respectively.