Gas-hydrate promotion by smectite–bioproduct interactions

Gas hydrates accumulate on the Gulf of Mexico seafloor around hydrocarbon seeps in waters sufficiently deep to provide adequate pressure/temperature combinations. High microbial activities occur around the hydrate accumulations. To understand apparent catalytic effects of bioproducts on hydrate formation, the mechanism of sII hydrate nucleation in unconsolidated porous media was investigated in our laboratory. Because smectite clays interacting with biopolymers had been shown to promote laboratory hydrates by decreasing induction times, increasing formation rates and altering morphology, these materials commonly found in near-surface sediments were selected for study as possible nucleating agents. Dynamic light scattering (DLS) with a helium–neon laser was used to measure particle diameters down to about 2 nm. Scanning electron microscopy (SEM) was utilized to verify particle sizes and to give additional information on biopolymer–clay associations. This paper presents evidence that nanometer-sized particles of mineral–bioproduct associations of about 80 nm–450 nm diameter may act as nucleation sites for hydrate crystal initiations in sediments and then remain dispersed throughout the accumulated hydrate mass. Emulsan biopolymer was shown by SEM to apparently unfold and associate with the smectite (nontronite) in a backbone arrangement and to give multiple hydrate nucleation sites along a linear network. SEM and DLS measurements were in agreement on particle sizes and shapes. X-ray diffraction suggested that biopolymer intercalates the smectite interlayer, probably driven by clay associations with biopolymer hydrophilic groups. It is hypothesized that hydrocarbon gases attach to biopolymer hydrophobic fatty-acid branches protruding from clay interlayers and subsequently facilitate hydrate structure formation by interacting with nearby water associated with the hydrophilic segments of the biopolymer.