Kinetic Studies of Methane–Ethane Mixed Gas Hydrates by Neutron Diffraction and Raman Spectroscopy

• Published in: The journal of physical chemistry. B Vol. 113; no. 15; pp. 5172 - 5180
• Main Authors: Murshed, M. Mangir, Kuhs, Werner F
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 16.04.2009
• Subjects: B: Statistical Mechanics, Thermodynamics, Medium Effects; Ethane - chemistry; Gases - chemistry; Kinetics; Methane - chemistry; Neutron Diffraction; Reference Standards; Scattering, Small Angle; Spectrum Analysis, Raman - methods; Spectrum Analysis, Raman - standards; Water - chemistry
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp810248s

In situ formations of CH4−C2H6 mixed gas hydrates were made using high flux neutron diffraction at 270 K and 5 MPa. For this purpose, a feed gas composition of CH4 and C2H6 (95 mol% CH4) was employed. The rates of transformation of spherical grains of deuterated ice Ih into hydrates were measured by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. Phase fractions of the crystalline constituents were obtained from Rietveld refinements. A concomitant formation of structure type I (sI) and structure type II (sII) hydrates were observed soon after the gas pressure was applied. The initial fast formation of sII hydrate reached its maximum volume and started declining very slowly. The formation of sI hydrate followed a sigmoid growth kinetics that slowed down due to diffusion limitation. This observation has been interpreted in terms of a kinetically favored nucleation of the sII hydrate along with a slow transformation into sI. Both powder diffraction and Raman spectroscopic results suggest that a C2H6-rich sII hydrate was formed at the early part of the clathration, which slowly decreased to ∼3% after a reaction of 158 days as confirmed by synchrotron XRD. The final persistence of a small portion of sII hydrate points to a miscibility gap between CH4-rich sI and C2H6-rich sII hydrates.