Experimental measurements and thermodynamic modeling of dissociation pressure of CO2 hydrate in sulfate solutions

Carbon capture and storage (CCS) has been a popular strategy to mitigate climate change and has attracted significant attention from both industry and academia. CO2 can be stored in the form of CO2 hydrate in deeper locations in an ocean, which makes it a potential option for CO2 sequestration. Dissolved salts in the ocean brine can significantly affect the dissociation pressure of CO2 hydrate. Sulfate salts are one of the most common salt species in the oceanic brine. Although various experimental studies have been conducted to investigate the phase behavior of CO2 hydrate in brine, few studies focus on the effect of sulfate salts on the dissociation pressure of CO2 hydrate. In this study, we build an in-house experimental setup to investigate the effect of monovalent and divalent sulfate salts on the dissociation pressure of CO2 hydrate. The dissociation pressure of CO2 hydrate in Na2SO4, K2SO4, MgSO4, and CuSO4 aqueous solutions is measured using the isochoric pressure search method at different concentrations over the temperature range of 274.36 - 282.15 K and the pressure range of 1.50 - 4.03 MPa. A hybrid methodology incorporating the Soave-Redlich-Kwong Equation of State (SRK EOS), the van der Waals-Platteeuw (vdW-P) model, and the Pitzer model is applied to predict the dissociation pressure of CO2 in sulfate solutions. In addition, the dissociation enthalpies of CO2 hydrate in these sulfate solutions are calculated using the Clausius-Clapeyron equation based on the measured dissociation points. The experimental results show that the dissociation pressure of CO2 hydrate in Na2SO4, K2SO4, and MgSO4 solutions is higher than that in pure water, and the dissociation pressure of CO2 hydrate in sulfate solutions increases with an increasing salt concentration. Conversely, CuSO4 barely affects the dissociation pressure of CO2 hydrate, which is mainly attributed to the lower molar concentration of the ions compared with the other salt solutions and the ion specificity of Cu2+. The prediction results are in alignment with the experimental data measured in this study, which proves the feasibility of the thermodynamic model in predicting the dissociation pressure of CO2 hydrate in sulfate solutions. Additionally, the calculated dissociation enthalpies of CO2 hydrate show a dependence on both temperature and salt concentration. It is also revealed that Cu2+ exhibits ion specificity in affecting the dissociation enthalpy of CO2 hydrate, likely due to its more distinct ability to impact the cage occupancy of CO2 hydrate than the other ions. These findings enhance our understanding of the impact of sulfate salts on the dissociation behavior of CO2 hydrate and offer valuable insights for CO2 sequestration.