Molecular behavior of hybrid gas hydrate nucleation: separation of soluble H₂S from mixed gas

Soluble H₂S widely exists in natural gas or oil potentially corroding oil/gas pipelines. Furthermore, it can affect the hydrate formation condition, resulting in pipeline blockage; the nucleation mechanism from mixed gas including H₂S is still largely unclear. Molecular dynamics simulations were performed to reveal the effects of different initial mixed H₂S/CH₄ compositions on the hydrate nucleation and growth process. The geometric details of the nanobubbles and gas composition in the nanobubbles were analyzed; the size of the nanobubbles was found to decrease from 3.4 nm to 1.4 nm. With the increase in the initial H₂S proportion, the diameter of the nanobubbles decreased; more guest molecules were dissolved in the water, which improved the initial concentration of guest molecules in the water. A multi-site nucleation process was observed, and separate hydrate clusters could grow independently until the simulation box limited their growth due to high local H₂S concentration as a potential nucleation location. When the initial proportion of mixed gas approaches, H₂S preferred to occupy and stabilize the incipient cage. Moreover, 5¹², 4¹5¹⁰6², and 5¹²6² cages accounted for approximately 95% of the first hydrate cage. Nucleation rates were shown to increase from 4.62 × 10²⁴ to 9.438 × 10²⁶ nuclei cm^-3 s^-1. The present high subcooling and H₂S concentration provided a high driving force to promote mixed hydrate nucleation and growth. The proportion of cages occupied by H₂S increased with increasing initial H₂S proportion, but the largest enrichment factor of 1.38 occurred at 10% initial H₂S/CH₄ mixed gas.