Tetrahydrofuran hydrate crystal growth inhibition by bis-and tris-amine oxides

• Bis- and tris-amine oxides have been investigated as tetrahydrofuran hydrate crystal growth inhibitors.
• They can be more effective as inhibitors than mono-amine oxides.
• Inhibition is better with n-butyl or iso-pentyl groups.
• The optimum inter-nitrogen distance is a chain of about 5–6 aliphatic carbon atoms.

Amine oxides are an alternative, non-ionic class of gas hydrate anti-agglomerant (AA) surfactants that are potentially more environmentally-friendly than cationic surfactant AAs. These classes of AAs work by interacting with hydrate crystal surfaces. Recently, we reported on the clathrate hydrate crystal growth inhibition of monoamine oxides using Structure II (SII) tetrahydrofuran (THF) hydrate (Kelland et al., 2012). It was determined that the best hydrate crystal growth inhibition was provided by amine oxides with n-butyl, n-pentyl or iso-pentyl groups, with tributylamine oxide being the best homofunctional trialkylamine oxide investigated. However, replacement of one butyl group with a larger group, forming the tail of an AA surfactant, lowered the inhibition significantly which could have consequences for the use of mono-amine oxides as AAs.We have now investigated bis-amine oxides and discovered that they can give even greater THF hydrate crystal growth inhibition than mono-amine oxides, particularly when the amine oxides have the correct size alkyl groups and are an optimum distance apart. The optimum alkyl group was found to be n-butyl and the optimum distance for bis-amine oxides is with a chain of 5–6 sp3 carbon atoms separating the nitrogen atoms. Alternatively, a heteroatom can be placed in this spacer chain, for example a third nitrogen atom, such as for alkylated derivatives of diethylenetriamine. These results mean that the use of bis-amine oxide surfactants could potentially lead to improved AA performance compared to mono-amine surfactants because of their greater adsorption onto hydrate surfaces. They may also act as improved synergists for polymeric kinetic inhibitors of natural gas hydrates.