Gas hydrate is one of the main concerns in the flow assurance issues for under water multiphase pipelines. Hydrate nucleation and growth in the water-in-oil emulsions have not been completely understood due to the complex factors, such as the composition of crude oils. Resins, as a common component in crude oil, can pose great effects on hydrate formation, which is still lack of investigation. This paper aims to bridge this gap with a custom-designed high pressure autoclave. Different with other hydrate investigation apparatus, an online viscometer was equipped for the real time viscosity measurement. Resins were separated from the Venezuelan residue for the purpose, following the saturates, aromatics, resins, and asphaltenes fractionation method. A series of experiments of hydrate formation were carried out in the emulsions with the presence of different resin contents, under the condition of 2.7 °C, 2.6 MPa, and 40 vol. % water cut.
It was observed that resins hindered hydrate formation in water-in-oil emulsions. The induction time increased with the increasing of resin content. The induction time in the emulsion with the presence of 1.0 wt. % resin content was almost 200 min longer than that in the emulsion without resins. It was found that an increase in resin concentration led to the significant reduction in temperature peak. In addition, a time delay phenomenon of temperature and pressure in the growth onset was found in the system with 0.5 or 1.0 wt. % resin content, by virtue of the online viscometer. It demonstrated the impeding effect of resins on hydrate growth. Moreover, the microphotographs of water-in-oil emulsions were obtained. It was observed that the resins can be adsorbed on the water droplet surface, and hence occupied the hydrate nucleation sites and formed a barrier for the further penetration of gas molecules. The adsorption phenomenon can preliminarily account for the inhibiting effect of resins on hydrate formation. It provides a scientific understanding for the effect of resins on hydrate formation in water-in-oil emulsions, excluding the interference of wax and other components. It would be useful to an appropriate flow assurance strategy designing for the under-water multiphase pipelines.