Clathrate hydrate formation in NaCl and MgCl2 brines at low pressure conditions

Abstract

Hydrate-based desalination (HBD) has been developed to obtain fresh water from seawater in an economic and environmental sustainable manner. As a low-pressure hydrate former for the HBD process, chlorodifluoromethane (R22) hydrates were formed in the pressure range of 1-6 bar under brine environments, aqueous NaCl and MgCl2 solutions. Synchrotron X-ray diffraction and Raman spectroscopy measurements revealed that the R22 hydrates formed with NaCl and MgCl2 show structure I and enclathration of R22 molecules into the large cages. These results also confirmed that the salt ions cannot be encaged in the gas hydrate framework, reflecting the ion exclusion behavior for HBD above the eutectic of water and hydrated salts. The formation kinetics of R22 clathrate hydrate in the presence of salts show that both the initial growth rate and pressure drop of the R22 hydrates heavily depend on the salinity of aqueous solutions. A new theoretical approach adopting the transient time-dependent apparent rate constant of hydrate formation with salts was proposed to predict the formation kinetics of R22 hydrates under brine environments, which was in good agreements with the experimental results. These results provide good information for separating ionic compounds from aqueous solutions by hydrate-based separation processes.