Effect of the Temperature and Tetrahydrofuran (THF) Concentration on THF Hydrate Formation in Aqueous Solution

Abstract

The knowledge of the mechanism of clathrate hydrate formation is crucial for studying the formation of a natural gas hydrate and developing hydrate-based technologies. In this study, low-field nuclear magnetic resonance (NMR) is applied to observe the processes of tetrahydrofuran (THF) hydrate formation from the solutions with different THF concentrations, and from the analysis of the NMR transverse relaxation time (T2) of hydrates and solutions, the formation mechanism of THF hydrate is discussed. A quantitative relationship between the NMR T2 spectral area and the mass of THF hydrate is established, and it is applied to estimate the hydrate amount in the formation process of THF hydrate. The results obtained show that T2 of THF solution is controlled by the temperature and THF concentration: longer at a higher temperature and shorter at a higher THF concentration. Moreover, the initial THF concentration does not affect the final concentration of the remaining solution after hydrate crystallization, and the formation of THF hydrate from solution follows the thermodynamics of solution reaction, with the THF concentration of the solution ending at the phase line after hydrate crystallization. The kinetics of THF hydrate formation is affected by the temperature and THF concentration: a higher formation rate in the solution with stoichiometric composition (19.06 wt % THF) of THF hydrate than either THF-rich or water-rich solution and a lower formation rate at a higher temperature.