Dual nature of methanol as a thermodynamic inhibitor and kinetic promoter of methane hydrate formation in a wide concentration range

• Published in: Journal of molecular liquids 2024-06, Vol.403, p.124780, Article 124780
• Main Authors: Semenov, Anton P., Tulegenov, Timur B., Mendgaziev, Rais I., Stoporev, Andrey S., Istomin, Vladimir A., Sergeeva, Daria V., Lednev, Daniil A., Vinokurov, Vladimir A.
• Format: Article
• Language: English
• Subjects: Hydrate growth; Hydrate nucleation; Kinetic hydrate inhibitor; Kinetic hydrate promoter; Methane hydrate; Thermodynamic hydrate inhibitor
• ISSN: 0167-7322
• DOI: 10.1016/j.molliq.2024.124780

[Display omitted] •Methanol (1–40mass%) promotes nucleation and growth of methane hydrate.•Mean hydrate onset subcooling is five times less for 20% MeOH compared to water.•Hydrate nucleation rate increases by an order of magnitude at 5% MeOH vs. water.•Methanol is a thermodynamic inhibitor and a kinetic promoter of methane hydrate.•The kinetic promotion function of methanol can be reversed at MeOH content ≥ 50 mass%. Methanol (MeOH) is a common thermodynamic inhibitor of gas hydrates. However, its impact on the kinetics of methane hydrate formation has not been systematically investigated. We have thoroughly examined the effect of MeOH in a wide concentration range on the nucleation and growth kinetics of methane hydrate. The onset temperature To and subcooling ΔTo of methane hydrate were determined under ramp cooling of 1 K/h. The mean To is not affected by methanol in the 0–2.5mass% range but decreases within 2.5–50mass%. At the same time, it was revealed that ΔTo for 1–40mass%MeOH is significantly smaller than that of water, making methanol a hydrate nucleation promoter within the concentration range. The relationship between ΔTo and the methanol concentration shows a minimum of 0.53 ± 0.36 K (at 20mass%). Adding 1–30mass% of methanol reduces the stochasticity of the methane hydrate nucleation events. The hydrate nucleation rate increases by an order of magnitude at 1.5 K subcooling when 5 % of MeOH is added to water. Besides, methanol enhances the methane hydrate growth at 1–40mass%, with the maximum rate occurring at 10mass% MeOH. Despite the excellent promoting properties of methanol, extrapolation suggests that MeOH may inhibit both nucleation and growth of methane hydrate in more concentrated solutions (≥50mass%). Methanol has a dual nature as a thermodynamic inhibitor and a kinetic promoter of methane hydrate formation. The kinetic promotion function of methanol is observed within a specific range (1–40mass%), but in more concentrated systems, it seems to be reversed.