Abstract

In this study, the dissociation behavior of CH4 hydrate in the absence and presence of poly(N-vinylcaprolactam) (PVCap) was closely investigated using a combination of experimental techniques, including in-situ Raman spectroscopy and high-pressure micro-differential scanning calorimetry (HP μ-DSC), and molecular dynamics (MD) simulations. The experimental results clearly demonstrated that CH4 hydrate dissociated more slowly and in two steps in the presence of PVCap. The MD simulations revealed that this slow and two-step dissociation was mainly due to the adsorption of PVCap onto the hydrate surface, which hindered the mass transfer of CH4 from the hydrate into the solution. The high viscosity and steric hindrance of PVCap also impeded the formation and growth of CH4 bubbles during the hydrate dissociation, contributing to the slower dissociation of CH4 hydrate in the PVCap solution. The broad and asymmetric shape of the last endothermic peak observed via HP μ-DSC was caused by the adsorption of PVCap during CH4 hydrate dissociation. The findings of this study provide valuable insights into the precise mechanism of hydrate dissociation in the presence of kinetic hydrate inhibitors.

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