Effects of a Quaternary Ammonium Salt on the Growth, Wettability, and Agglomeration of Structure Ⅱ Hydrate Crystals

摘要

This work studied the effects of a water-soluble quaternary ammonium salt (called DA 50) on the growth, wettability, and agglomeration of cyclopentane (CP) hydrate crystals and methane (CH4)/propane (C3H8) hydrate crystals. The impact on these properties of adding 4 wt % NaCl to the DA 50 solution was also investigated. The hydrates were formed from water/CP, water/(CP + n-octane (n-C8)), and water/(CP + n-dodecane (n-C12)) mixtures at atmospheric pressure and from a water-C8/(CH4 + C3H8) mixture under pressure (about 67 bar). Experiments were performed at a subcooling of 6 degrees C in the case of the CP hydrates and 9-10 degrees C in the case of the CH4/C3H8 hydrates. In both hydrate systems, adding NaCl to the surfactant solution of 0.1 or 1 wt % DA 50 led to the formation of individual oil-wettable pyramidal crystals. Without salt, the hydrate formed a water-wettable shell that covered the water/oil interface just as the system without surfactant did. The antiagglomeration performance of the 1 wt % DA 50 solution was evaluated by performing torque measurements in an agitated batch reactor at a water cut of 30 vol %. Without NaCl, torque increased with the amount of CP hydrates. The system formed a nonflowable jelly-like phase, with water as the continuous phase, until a phase inversion occurred. From there on torque significantly decreased and the system became a flowable dispersion of large hydrate particles (similar to 700 mu m) in the CP phase. With 4 wt % NaCl, the system consisted of small (similar to 70 mu m) hydrate particles dispersed in the CP phase and the torque signal remained constant throughout the hydrate crystallization process. The torque profiles obtained at concentrations of 0 or 4 wt % NaCl for the CP hydrates and the CH4/C3H8 hydrates were similar, suggesting analogous states for both systems. For both hydrate systems, adding NaCl to the DA 50 solution led to the formation of oil-wettable hydrates and drastically improved the antiagglomeration performance of the surfactant molecules, revealing a correlation between the formation of individual crystals and the antiagglomeration performance of the surfactant. The similarity between the growth patterns and shapes of the CP-hydrate crystals and the CH4/C3H8-hydrate crystals confirmed that CP hydrates are an interesting model for evaluating the antiagglomeration performance of surfactants.