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The mechanisms by which hydrates deposit in a petroleum production line are related to pipeline surface properties, fluid composition and properties, and water cut. In this work, adhesion forces between cyclopentane hydrates and solid surfaces were investigated as a function of the solid material, the presence of water and the presence of petroleum acids in the oil phase. The influence of dissolved water on hydrate adhesion forces was also investigated. The results show that the adhesion force between hydrates and solid surfaces was dependent on the surface material; solids with low surface free energy lead to the lowest adhesion forces. The adhesion force was strongly dependent on the presence of water in the system. When a water drop was deposited on the solid surface, the adhesion force between the hydrate and the solid surface was more than 10 times larger than hydrate-hydrate adhesion forces. The presence of a water-saturated oil phase also led to an increase in adhesion force between hydrate particles. Adhesion forces were highest when the solid surfaces are water-wet. Addition of petroleum acids to the oil phase drastically reduced adhesion forces.

Cyclopentane (CyC5) hydrate interparticle adhesion force measurements in the presence of small amounts of crude oil (up to 8 wt % in cyclopentane) were performed at 3.2 °C, under atmospheric pressure, using a micromechanical force apparatus. The adhesion forces obtained for cyclopentane hydrate in small amounts of crude oil in CyC5 bulk fluid were lower than those measured for CyC5 hydrate in pure CyC5 bulk fluid. CyC5 hydrate-normalized adhesive forces were measured to be on the order of 0.5 mN/m for samples containing approximately 5−8 wt % of Caratinga and Troika crude. Hydrate-normalized adhesive forces were found to increase when the surface-active components (including acids and asphaltenes) were removed from the crude oil. These results suggest that crude oils with high contents of acids and asphaltenes may be more likely to exhibit nonplugging tendencies in oil and gas flowlines.

Adhesion forces between cyclopentane hydrate particles were measured at atmospheric pressure and 3.2 °C using an improved micromechanical force apparatus. Because of the complexity of crude oil systems, a series of model oils was prepared by adding surface-active components to 200 cP mineral oil as analogues to crude oil systems. The addition of 1 wt % sorbitan monooleate (Span80, a commercial anti-agglomerant), 1 wt % polypropylene glycol (an amphiphilic polymer), and 0.6 wt % commercial naphthenic acid mixture, separately, to a mineral oil and cyclopentane continuous phase, reduced the average interparticle hydrate adhesion force by 37, 65, and 80%, respectively, compared to pure mineral oil and cyclopentane. The 95% confidence bounds of the Span80 and mineral oil data points overlap; therefore, we cannot conclude that Span80 was effective at reducing the adhesion force between hydrate particles. These results indicate that model amphiphilic polymers and commercial naphthenic acid mixtures may be surface-active on the hydrate particle, drastically reducing the agglomeration tendency between hydrate particles; naphthenic acids are found to be the most effective at lowering the adhesive force between particles. The structure of the additive plays a role in determining the extent of surface activity and effectiveness. Compounds with small hydrophilic groups can more efficiently adsorb to the hydrate surface, while additives that induce morphological changes to the hydrate surface may cause non-uniform growth and are more effective in preventing hydrate agglomeration.

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