Abstract: Hydrate crystals growth on the surface of methane bubble (hydrate film) in pure water was studied by using a high-pressure visible microscope under the conditions of subcooling ΔT = 5.44–13.72 K and methane concentration difference ΔC = 2.92–8.19 mol·L^-1. It was found the hydrate film is porous and the hydrate crystals grow towards the liquid phase on the film substrate. The crystal morphology and growth rate are affected by ΔT and ΔC. When ΔT < 8.82 K and ΔC < 4.12 mol·L^-1, the hydrate grows into scattered columnar crystals, and the axial growth rate of the crystal gradually decreases. When ΔT > 8.82 K or ΔC > 4.12 mol·L^-1, the hydrate crystals grow in dendritic shape, and the axial growth rate increases first and then decreases. The perimeter and area of the growing hydrate crystals were measured, and the fractal dimension of hydrate crystal under different ΔC and ΔT was calculated. The results show that the fractal dimension of columnar hydrate crystal is greater than 3. When 3.87 mol·L^-1 < ΔC < 4.20 mol·L^-1 and 7.4 K < ΔT < 8.8 K, the fractal dimension of columnar hydrate crystal is greater than 4; The fractal dimension of dendritic hydrate crystal is less than 3. When ΔC > 4.77 mol·L^-1, ΔT < 8.52 K, the fractal dimension of dendritic hydrate crystal is less than 2.

Key words: Methane, Hydrate, Crystal growth, Morphology, Fractal dimension

摘要： Hydrate crystals growth on the surface of methane bubble (hydrate film) in pure water was studied by using a high-pressure visible microscope under the conditions of subcooling ΔT = 5.44–13.72 K and methane concentration difference ΔC = 2.92–8.19 mol·L^-1. It was found the hydrate film is porous and the hydrate crystals grow towards the liquid phase on the film substrate. The crystal morphology and growth rate are affected by ΔT and ΔC. When ΔT < 8.82 K and ΔC < 4.12 mol·L^-1, the hydrate grows into scattered columnar crystals, and the axial growth rate of the crystal gradually decreases. When ΔT > 8.82 K or ΔC > 4.12 mol·L^-1, the hydrate crystals grow in dendritic shape, and the axial growth rate increases first and then decreases. The perimeter and area of the growing hydrate crystals were measured, and the fractal dimension of hydrate crystal under different ΔC and ΔT was calculated. The results show that the fractal dimension of columnar hydrate crystal is greater than 3. When 3.87 mol·L^-1 < ΔC < 4.20 mol·L^-1 and 7.4 K < ΔT < 8.8 K, the fractal dimension of columnar hydrate crystal is greater than 4; The fractal dimension of dendritic hydrate crystal is less than 3. When ΔC > 4.77 mol·L^-1, ΔT < 8.52 K, the fractal dimension of dendritic hydrate crystal is less than 2.

关键词: Methane, Hydrate, Crystal growth, Morphology, Fractal dimension