화학공학소재연구정보센터
Energy & Fuels, Vol.34, No.11, 14034-14045, 2020
Phase Stability Conditions of the Methane plus Tetrabutylphosphonium Bromide plus Water Semiclathrate Hydrate System in the Presence and Absence of NaCl and/or MgCl2: Experimental Measurements and Thermodynamic Modeling
Gas hydrate, or clathrate hydrate, technology is considered to be one of the promising solutions for natural gas storage and transportation. Tetrabutylphosphonium bromide (TBPB) is capable of sorting out stability issues of hydrate formation effectively. On the other hand, using water from natural resources such as sea, river, or well instead of pure water is essential for hydrate formation in the industrial scale. The current study was organized to investigate the hydrate phase behaviors of CH4 + TBPB formed in saline solutions, which are necessary for potential industrial applications. For this purpose, we first generated hydrate dissociation conditions data of the CH4 + TBPB aqueous solution system over TBPB mass fractions of 0.05 and 0.2. It should be mentioned that there is some discrepancy between hydrate dissociation condition data of the CH4 + TBPB + water system reported in literature, which necessitates generation of accurate and reliable data in this work. Afterward, the effects of the presence of NaCl, MgCl2, and NaCl + MgCl2 in aqueous solutions on the hydrate dissociation conditions of the CH4 + TBPB + water system were studied. All equilibrium points were obtained using a reliable constant-volume pressure-search method in the pressure and temperature ranges of 1-5.5 MPa and 280-292 K, respectively. The experimental results show that the aforementioned salts have dual effects on the hydrate phase stability, depending on TBPB concentration in the aqueous solution. In the case of 0.05 mass fraction of TBPB in the aqueous solution, the presence of NaCl (0.05 mass fraction), MgCl2 (0.05 mass fraction), and NaCl + MgCl2 (0.05 + 0.05 mass fractions) can boost the hydrate stability conditions of the CH4 + TBPB + water system and can act as thermodynamic promoters. However, by increasing the TBPB mass fraction in aqueous solution to 0.20 mass fraction, the aforementioned salts can shift the hydrate stability conditions to high pressures/low temperatures and can act as thermodynamic inhibitors. Furthermore, the experimental results show that the thermodynamic inhibition effects of the mineral salts are higher when the pressure of hydrate formation increases. A thermodynamic model based on the van der Waals-Platteeuw (vdW-P) solid solution theory was also developed for the aforementioned systems. The model employs the Soave-Redlich-Kwong equation of state and the Bromley equations for the gas phase and the aqueous phase, respectively. Results show that the thermodynamic model is capable of predicting the hydrate dissociation conditions with acceptable accuracy.