Detecting Gas Hydrate Behavior in Crude Oil Using NMR
and Walter G. Chapman*
Chemical Engineering Department, Rice Uni
ersity, Houston, Texas 77251, and Petroleum Engineering Department, Texas Tech Uni
ersity, Lubbock, Texas 79406 Recei
ed: September 6, 2005; In Final Form: January 30, 2006
Because of the associated experimental difficulties, natural gas hydrate behavior in black oil is poorly understooddespite its grave importance in deep-water flow assurance. Since the hydrate cannot be visually observed inblack oil, traditional methods often rely on gas pressure changes to monitor hydrate formation and dissociation.Because gases have to diffuse through the liquid phase for hydrate behavior to create pressure responses, thecomplication of gas mass transfer is involved and hydrate behavior is only indirectly observed. This pressuremonitoring technique encounters difficulties when the oil phase is too viscous, the amount of water is toosmall, or the gas phase is absent. In this work we employ proton nuclear magnetic resonance (NMR)spectroscopy to observe directly the liquid-to-solid conversion of the water component in black oil emulsions.The technique relies on two facts. The first, well-known, is that water becomes essentially invisible to liquidstate NMR as it becomes immobile, as in hydrate or ice formation. The second, our recent finding, is that inhigh magnetic fields of sufficient homogeneity, it is possible to distinguish water from black oil spectrally bytheir chemical shifts. By following changes in the area of the water peak, the process of hydrate conversioncan be measured, and, at lower temperatures, the formation of ice. Taking only seconds to accomplish, thismeasurement is nearly direct in contrast to conventional techniques that measure the pressure changes of thewhole system and assume these changes represent formation or dissociation of hydrates
rather than simplychanges in solubility. This new technique clearly can provide accurate hydrate thermodynamic data in black oils. Because the technique measures the total mobile water with rapidity, extensions should prove valuablein studying the dynamics of phase transitions in emulsions.
When natural gases come into contact with water under highpressures and low temperatures, they form ice-like crystallinecompounds called gas hydrates, which are composed of nano-scale water cages that enclose gas molecules of appropriatediameters.
first realized it was gas hydrates,not ice, that were plugging natural gas pipelines. This markedthe beginning of the industrial interest in gas hydrates for flowassurance, i.e., assurance of unrestricted flow of fluids throughpipelines. Due to the frequent presence of water and lighthydrocarbons, such as methane, during oil production, hydrateplug formation is a serious concern in deep-water flow-assuranceof oil and gas flow lines, where high pressures and lowtemperatures are often encountered. To prevent hydrate plug-ging, appropriate amounts of chemical hydrate inhibitors areoften added into the pipelines or thermal insulations are installedto prevent heat loss. It was estimated that industry is spendingover 500 million dollars on hydrate inhibitors annually.
Thedose rates of hydrate inhibitors and thermal insulation designsare all based on the expected pipeline conditions relative to thehydrate phase diagram.
Therefore, accurate phase diagrams of gas hydrates are essential to safety and economic considerations.Equally important are hydrate formation and dissociationkinetics, key factors in hydrate management. Unfortunately,current models for predicting hydrate phase behavior showconsiderable discrepancy with experimental data for black oilsystems.
The differences can be as much as 5
which will either invoke unnecessary expense or put theoperation at great risk. New, accurate experimental data areneeded to test and tune phase behavior models.
However,hydrate phase behavior in black oil, particularly with emulsions,is poorly understood due to the associated experimental dif-ficulties. No kinetic data on gas hydrates in black oil has beenreported in the literature.In multihydrate-former systems, such as natural gas and black oil, the hydrate thermodynamic point is defined as the equilib-rium condition at which the last hydrate crystal dissociates.
Because the nature of black oil deters direct visual observation,traditional attempts to characterize hydrate behavior in black oil have frequently depended on monitoring system pressurechanges.
In this method, water, black oil, and gas are chargedinto a high-pressure cell. The pressure is monitored as this closedsystem is ramped in temperature. Because the gases have totransport through the liquid oil and water phase, some meansof mechanical stirring are often employed to facilitate the gasmass transfer. Pressure drops dramatically upon hydrate forma-tion because hydrate formation consumes large quantity of gas.After hydrate formation, the temperature is raised to dissociatethe hydrate. As hydrate dissociates, gases are released andpressure increases significantly. The transition point thatindicates complete hydrate dissociation (normally where pressureand temperature return to the original
curve before hydrateformation) is identified as the hydrate thermodynamic point.This traditional pressure
temperature monitoring techniqueis widely used but has some inherent limitations. For example,it can be troublesome in obtaining accurate hydrate thermody-
* Corresponding authors. Waylon.House@ttu.edu; firstname.lastname@example.org
Texas Tech University.
J. Phys. Chem. B
655210.1021/jp055039a CCC: $33.50 © 2006 American Chemical SocietyPublished on Web 03/16/2006