Measurements of solidification kinetics for benzene in methane at high pressures and cryogenic temperatures

A stirred, high-pressure, visual microscopy-based apparatus was used to investigate solid-formation kinetics in LNG-relevant binary mixtures. The apparatus can detect solid crystals as small as 20 µm in a 3.5 mm field of view and is capable of measurements at temperatures as low as 90 K and pressures up to 20 MPa. The apparatus is described in detail and is presented alongside experimental results for two benzene + methane mixtures. Measurements of the solid–fluid equilibrium temperatures for the benzene + methane mixtures at 10 MPa were determined by raising the temperature of the mixture in (0.5 to 1) K steps and observing whether the crystals were still present after 2 h. The equilibrium temperatures were consistent with those predicted using the software package ThermoFAST within the combined experimental and model uncertainties. Formation measurements were carried out using a 100 ppm benzene-in-methane sample. Isobaric constant-cooling experiments at pressures of 8 and 10 MPa were used to construct subcooling formation-probability distributions for this mixture by identifying the temperature at which solid crystals were first observed to form on a copper substrate. The subcooling values at formation ranged from (4.4 to 11.0) K and were used to generate a cumulative probability of formation. The measured formation-probability distribution was fit to a model based on Classical Nucleation Theory to yield an estimate of 5 mJ/m² for the effective surface free energy of solid benzene in liquid methane on the copper substrate. These results pave the way to probabilistic estimates of risk for solids formation in cryogenic heat exchangers.