Water Bridges in Clay Nanopores: Mechanisms of Formation and Impact on Hydrocarbon Transport

Abstract

Clays are prevalent in the earth's crust and usually deposited in the presence of water. An unusual finding in clays is that under certain conditions, water molecules can collectively form a bridge across a clay-hosted pore. However, there are relatively few studies focused on the formation mechanism of the water bridge in clay nanopores. In this work, we use molecular dynamics simulations to investigate the formation of the water bridge and its influence on fluid transport in slit-shaped illite nanopores. Two different basal illite surface chemistries are constructed: potassium− hydroxyl (P−H) and hydroxyl−hydroxyl (H−H) structures. Because pore size and water concentration are expected to control the formation of the water bridge, our simulations span a wide range of pore sizes and water concentrations. Generally, positive potassium layers and negative hydroxyl groups in P−H nanopore can induce partial charges which in return produce instant and local electric fields, favoring the formation of the water bridge. In P−H nanopores, the water bridge happens at a relatively low water concentration. However, in H−H nanopores, the water bridge only forms at high water concentrations. Additionally, smaller pore sizes favor the formation of water bridges. However, the presence of an electric field promotes the formation of a water bridge even in larger pore sizes in P−H pores. The results also indicate that in both P−H and H−H nanopores, water adsorption films initially create a smooth surface to promote the hydrocarbon flow. In P−H nanopores, further increases in the water concentration causes a sharp decline in the self-diffusion coefficients of the hydrocarbon and water due to the formation of the water bridge. The presence of electric fields in P−H pores can however weaken the confinement effect of illite and promote the hydrocarbon flow. In contrast, in H−H nanopores, the self-diffusion coefficients decline slowly with the increase of water concentration. This is because no water bridge is formed at low water concentrations in H−H nanopores.

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