Laura E. Dieker

Adhesion force between cyclopentane hydrates and solid surface materials

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.

Investigation of the Hydrate Plugging and Non-Plugging Properties of Oils

Three laboratories (Norwegian Institute of Science and Technology [NTNU], Institut Français du Pétrole [IFP], and the Colorado School of Mines [CSM]) determined hydrate plug formation characteristics in three oils, each in three conditions: (1) in their natural state, (2) with asphaltenes removed, and (3) with naturally occurring acids removed from the oil. The objective was to determine the major variables that affect hydrate plugging tendencies in oil-dominated systems, to enable the flow assurance engineer to qualitatively assess the tendency of an oil to plug with hydrates. In the past, it was indicated that chemical effects, for example, water-in-oil/hydrate-in-oil (emulsion/dispersion) stability, prevented hydrate plugs. For example, deasphalted oils provided low emulsion/dispersion stability and thus hydrate particles aggregated. In contrast pH 14-extracted oils were reported to remove stabilizing naphthenic acids, causing asphaltene precipitation on water/hydrate droplets, stabilizing the emulsion/dispersion to prevent aggregation and pluggage. This work suggests that in addition to chemistry, shear can enable plug-free operation in the hydrate region. High shear can prevent hydrate particle aggregation, while low shear encourages particle aggregation and plugging. As a result, flow assurance engineers may be able to forecast hydrate plug liability of an oil by a combination of chemistry and flow variables, such as: a) measurements of live oil emulsion stability, b) predictions of flow line shear, and c) knowledge of water cut. Plug formation qualitative trends are provided for the above three variables. Implications for flow assurance are given.

Assessing the feasibility of hydrate deposition on pipeline walls--adhesion force measurements of clathrate hydrate particles on carbon steel.

Adhesive forces between cyclopentane (CyC5) hydrates and carbon steel (CS) were measured. These forces were found to be substantially lower than CyC5 hydrate-CyC5 hydrate particle measurements and were also lower than ice-CS measurements. The measured adhesive forces were used in a force balance to predict particle removal from the pipeline wall, assuming no free water was present. The force balance predicted entrained hydrate particles of 3 microns and larger diameter would be removed at typical operating flow rates in offshore oil and gas pipelines. These predictions also suggest that hydrate deposition will not occur in stabilized (cold) flow practices.

MICROMECHANICAL ADHESION FORCE MEASUREMENTS BETWEEN CYCLOPENTANE HYDRATE PARTICLES

Cyclopentane hydrate interparticle adhesion force measurements were performed in pure cyclopentane liquid using a micromechanical force apparatus. Cyclopentane hydrate adhesion force measurements were compared to those of cyclic ethers, tetrahydrofuran and ethylene oxide, which were suspected to be cyclic ether-lean and thus contain a second ice phase. This additional ice phase led to an over-prediction of the hydrate interparticle forces by the capillary bridge theory. The adhesion forces obtained for cyclopentane hydrate at atmospheric pressure over a temperature range from 274-279 K were lower than those obtained for the cyclic ethers at similar subcoolings from the formation temperature of the hydrate. The measured cyclopentane interparticle adhesion forces increased linearly with increasing temperature, and are on the same order of magnitude as those predicted by the Camargo and Palermo rheology model.

HYDRATE PARTICLES ADHESION FORCE MEASUREMENTS: EFFECTS OF TEMPERATURE, LOW DOSAGE INHIBITORS, AND INTERFACIAL ENERGY

Micromechanical adhesion force measurements were performed on tetrahydrofuran (THF) hydrate particles in n-decane. The experiments were performed at atmospheric pressure over the temperature range 261–275 K. A scoping study characterized the effects of temperature, anti-agglomerants, and interfacial energy on the particle adhesion forces. The adhesion force between hydrate particles was found to increase with temperature and the interfacial energy of the surrounding liquid. The adhesion force of hydrates was directly proportional to the contact time and contact force. Both sorbitan monolaurate (Span20) and poly-Nvinyl caprolactam (PVCap) decreased the adhesion force between the hydrate particles. The measured forces and trends were explained by a capillary bridge between the particles.

Experimental Investigation of Deposition and Wall Growth in Water Saturated Hydrocarbon Pipelines in the Absence of Free Water

Using a combination of micromechanical force and flowloop measurements, hydrate deposition on a pipe wall surface was investigated for ‘dry’ hydrates formed in the bulk phase and for hydrates growing on the pipe surface. Cyclopentane ‘dry’ hydrates (without a free water phase) were used to predict whether hydrates, formed in a bulk condensate phase, would adhere to a pipe wall. Adhesion forces between cyclopentane hydrates and steel were measured using a micro-mechanical force apparatus. The average force of adhesion was measured to be very small, less than 0.01 N/m. This force was used in a particle force balance, predicting that hydrates formed in the bulk phase would not deposit on the pipe wall. It was hypothesized than in the presence of a water saturated hydrocarbon, hydrates would grow on the pipe wall as the fluid cooled below its equilibrium temperature. This hypothesis was confirmed using a single pass condensate flowloop. Water was continuously dissolved into the flowloop inlet stream as water deposited in the flowloop test section, resulting in both a pressure drop and fluid temperature increase. This work illustrates the need for a hydrate wall growth