Interactions of clathrate hydrate promoters sodium dodecyl sulfate and tetrahydrofuran investigated using 1H diffusion nuclear magnetic resonance at hydrate-forming conditions

Abstract

Thermodynamic hydrate promoters and kinetic hydrate promoters can be used to reduce the P–T conditions for clathrate hydrate synthesis to decrease the nucleation induction time while increasing growth rates. Two commonly used promoters for hydrate research are tetrahydrofuran (THF) and sodium dodecyl sulfate (SDS), which can increase the overall hydrate promotion when used in tandem as compared to individually. There are several molecular theories regarding how SDS promotes hydrate growth. This study explores the micellular theory, for which hydrate formation depends on surfactant aggregates (micelles) at a critical micelle concentration (CMC) to increase the interfacial surface area. The micellular theory is the most investigated and criticized surfactant hydrate promotion theory. To address questions related to micellar behavior, this study investigates the intermolecular behavior between SDS and THF for the identification of micelles at hydrate-forming conditions. The systems explored contained THF at 3 and 5 wt. % with varying concentrations of SDS below and above the CMC. Several methods including a qualitative visual method, conductivity, interfacial tensiometry, 13C Liquid-state Nuclear Magnetic Resonance (NMR) spectroscopy, and 1H diffusion NMR spectroscopy were evaluated at temperatures below the Krafft point of SDS and above 0 °C. The presence of THF at low concentrations decreased the critical temperature for the formation of SDS micelles, where SDS is solubilized in THF/water solution at hydrate-forming temperatures without precipitation. The CMC of SDS was decreased significantly even at hydrate-forming conditions. Mixed surfactant–cosolvent micellular behavior of SDS in the presence of low concentrations of THF was confirmed at hydrate-forming conditions above 0 °C.