Yu Zhang,Lei Zhang,Chang Chen,Hao-Peng Zeng,Xiao-Sen Li,Bo Yang
The equilibrium and kinetic of hydrate in sediments can be affected by the presence of external components like bentonite with a relatively large surface area. To investigate the hydrate formation and decomposition behaviors in bentonite clay, the experiments of methane hydrate formation and decomposition using the multi-step decomposition method in bentonite with different water contents of 20%, 40% and 60% (mass) were carried out. The contents of bound, capillary and gravity water in bentonite clay and their roles during hydrate formation and decomposition were analyzed. In bentonite with water content of 20% (mass), the hydrate formation rate keeps fast during the whole formation process, and the final gas consumption under different initial formation pressures is similar. In bentonite with the water contents of 40% and 60% (mass), the hydrate formation rate declines significantly at the later stage of the hydrate formation. The final gas consumption of bentonite with the water contents of 40% and 60% (mass) is significantly higher than that with the water content of 20% (mass). During the decomposition process, the stable pressure increases with the decrease of the water content. Hydrate mainly forms in free water in bentonite clay. In bentonite clay with the water contents of 20% and 40% (mass), the hydrate forms in capillary water. In bentonite clay with the water content of 60% (mass), the hydrate forms both in capillary water and gravity water. The bound water of dry bentonite clay is about 3.93% (mass) and the content of capillary water ranges from 42.37% to 48.21% (mass) of the dry bentonite clay.
Hydrophobic anti-wetting membranes have many applications, such as oily wastewater treatment via oil/water separation, desalination via membrane distillation, and carbon capture via gas-liquid membrane contactors. Herein, we used a simple and scalable method to fabricate robust superhydrophobic polyvinylidene fluoride (PVDF) based membranes by one-step spray-coating of fluorinated SiO 2 nanoparticles. The prepared PVDF membrane was systematically characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and contact angle measurements. The modified PVDF membrane had excellent superhydrophobicity with an extremely high water contact angle up to 171.8 ± 1.1° and a low sliding angle of 1.69 ± 0.13°, due to the fluorinated close-packed hydrophobic SiO 2 nanoparticles on the surface. The modified PVDF membrane maintained its relatively stable superhydrophobicity under various harsh conditions, i.e., exposure in hot water, NaOH and HCl, ultrasonication and high-speed flushing, indicating the superior robustness and stability. The prepared membrane also exhibited consistent separation efficiencies up to 99.88 ± 0.03% in water-in-oil emulsions, and superior recyclability and durability over 40 cycles. In addition, spray-coating showed its great promise in engineering various superhydrophobic surfaces on different substrates and excellent scalability in fabricating large-size membranes. This study demonstrates a facilely scalable spray-coating method for engineering robust superhydrophobic surfaces and membranes that can be potentially used for various gas, vapor and water/oil separations.