Formation and evolution of nanobubbles in CH4-H2O-Alcohol system: Insight into the effect of alcohol chain length from molecular dynamics simulations

Abstract

Nanobubbles (NBs) which are gas filled cavities of nanometre dimensions present in liquids attracted increasing attention in the recent years due to their application in various fields such as chemistry, biology, medicine etc. An important aspect of NB research is the study of effect of additives on formation and evolution of these bubbles. The present study examined by applying molecular dynamics simulations, the formation and evolution of methane NBs in the CH4-H2O-Alcohol system, which is known to form during alcohol induced dissociation of CH4 hydrates in the natural gas extraction process. The effect of alcohol type and concentration on NB formation and evolution was examined through simulations of CH4-H2O-CH3OH, CH4-H2O-C2H5OH and CH4-H2O-nC3H7OH systems. The study revealed that increase in both concentration and the alkyl chain length of alcohols promoted NB formation. Alcohol molecules are found to enhance NB nucleation through accumulation near the NB-liquid interface resulting in a decrease in the surface tension (γ) at the interface. These effects become more pronounced as the alkyl chain length increases which explains the enhanced NB formation in systems containing nC3H7OH and C2H5OH compared to those containing CH3OH. The mechanism of formation and evolution of NBs is found to significantly depend on the type of alcohol present. NBs are found to nucleate at multiple locations in the systems containing nC3H7OH and C2H5OH which eventually coalesce to form a single large stable NB. In the presence of NBs which vary significantly in size, bubble growth was also found to occur through Ostwald ripening which involves transfer of CH4 from smaller NB to the larger one. In contrast, in the CH4-H2O-CH3OH system, primarily a single NB nucleated which grew in size through absorption of CH4 molecules dissolved in the liquid, rather than through coalescence or Ostwald ripening. The observed influence of alcohol type on the process of NB evolution is explained by examining the influence of alkyl chain length on γ and diffusivity of CH4 molecules. Due to the role of NBs on methane hydrate regeneration from the hydrate melt, we examined the influence of NB in the CH4-H2O-Alcohol system on the organization of water molecules (HSWs) present in the hydration shell of dissolved CH4. The value of F4 order parameter of HSWs and the number of hydrogen bonded water rings in the hydration shell of CH4 were analysed. The value of F4 order parameter indicate that the hydrophobic alkyl chain of alcohol induced hydrate like arrangement of HSWs, which is more pronounced in the case of alcohol with longer alkyl chain. However, alcohol molecules are also found to dislodge HSWs around CH4 resulting in a decrease in the number of water rings around dissolved CH4 which is not conducive to hydrate formation. These observations are consistent with the reported dual effect of alcohol on hydrate formation with alcohol promoting hydrate formation at low concentrations and inhibiting at high concentrations.