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UBC Theses and Dissertations

The effect of surfactant on the morphology of methane/propane clathrate hydrate crystals Yoslim, Jeffry


Considerable research has been done to improve hydrate formation rate. One of the ideas is to introduce mechanical mixing which later tend to complicate the design and operation of the hydrate formation processes. Another approach is to add surfactant (promoter) that will improve the hydrate formation rate and also its storage capacity to be closer to the maximum hydrate storage capacity. Surfactant is widely known as a substance that can lower the surface or interfacial tension of the water when it is dissolved in it. Surfactants are known to increase gas hydrate formation rate, increase storage capacity of hydrates and also decrease induction time. However, the role that surfactant plays in hydrate crystal formation is not well understood. Therefore, understanding of the mechanism through morphology studies is one of the important aspects to be studied so that optimal industrial processes can be designed. In the present study the effect of three commercially available anionic surfactants which differ in its alkyl chain length on the formation/dissociation of hydrate from a gas mixture of 90.5 % methane – 9.5% propane mixture was investigated. The surfactants used were sodium dodecyl sulfate (SDS), sodium tetradecyl sulfate (STS), and sodium hexadecyl sulfate (SHS). Memory water was used and the experiments for SDS were carried out at three different degrees of under-cooling and three different surfactant concentrations. In addition, the effect of the surfactant on storage capacity of gas into hydrate was assessed. The morphology of the growing crystals and the gas consumption were observed during the experiments. The results show that branches of porous fibre-like crystals are formed instead of dendritic crystals in the absence of any additive. In addition, extensive hydrate crystal growth on the crystallizer walls is observed. Also a “mushy” hydrate instead of a thin crystal film appears at the gas/water interface. Finally, the addition of SDS with concentration range between 242ppm – 2200ppm (ΔT =13.10C) was found to increase the mole consumption for hydrate formation by 14.3 – 18.7 times. This increase is related to the change in hydrate morphology whereby a more porous hydrate forms with enhanced water/gas contacts.

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