The aim of this study was to determine the influence of four inorganic salts, KCl, NaCl, KBr and NaBr, on the thermodynamic conditions of methane hydrate formation. In order to achieve this, the vapor–liquid water-hydrate (VL_WH) equilibrium conditions of methane (CH₄) hydrate were measured in the temperature range of 274.15 K–282.15 K by the isothermal pressure search method. The results demonstrated that, in comparison with deionized water, the four inorganic salts exhibited a significant thermodynamic inhibition on CH₄ hydrate. Furthermore, the inhibitory effect of Na⁺ on methane hydrate is more pronounced than that of K⁺, where there is no discernible difference between Cl⁻ and Br⁻. The dissociation enthalpy ($∆H_{diss}$) of CH₄ hydrate in the four inorganic salt solutions is comparable to that of deionized water, indicating that the inorganic salt does not participate in the formation of hydrate crystals. The Chen–Guo hydrate model and N–NRTL–NRF activity model were employed to forecast the equilibrium conditions of CH₄ hydrate in electrolyte solution. The absolute relative deviation (AARD) between the predicted and experimental values were 1.24%, 1.08%, 1.18% and 1.21%, respectively. The model demonstrated satisfactory universality and accuracy. This study presents a novel approach to elucidating the mechanism and model prediction of inorganic salt inhibition of hydrate.

Carbon capture, utilization and storage are facilitated through carbon dioxide (CO₂) transport. Pipe transportation is the main method for transporting CO₂. However, hydrate blockages reduce transport efficiency in the pipelines, and the throttling devices are the main location of hydrate blockages. In this paper, the mechanism of hydrate formation in the throttling of CO₂-containing trace moisture was investigated. The throttling device in a pipe was mimicked using a cylindrical orifice plate. The work also studied the effects of moisture content, upstream pressure and upstream temperature on hydrate formation. The results indicate that the Joule–Thomson cooling effect is a key contributor, and promotes the condensation of trace moisture, resulting in the free water necessary for hydrate nucleation. Under the effect of gas flow back-mixing, it is easy for the hydrate to adhere to the inner surface of the pipe behind the orifice plate. When the moisture content in the gas increases from 123 μmol/mol to 1024 μmol/mol, the hydrate induction time decreases from infinity to 792 s. However, the moisture content has no effect on the adhesion strength of the hydrate to the inner surface of the pipe. When the initial upstream pressure increases from 2.0 MPa to 3.5 MPa, the hydrate induction time decreases from infinity to 306 s. When the upstream temperature decreases from 291.15 K to 285.15 K, the hydrate induction time decreases from infinity to 330 s. With the decrease in the initial upstream temperature, the adhesion of hydrate particles to the inner surface of the pipe is promoted. This study provides experimental evidence for the characteristics of hydrate formation in the process of CO₂ throttling.

Hydrate-based gas separation (HBGS) has good potential in the separation of helium from helium-rich natural gas. HBGS should be carried out under a pressure higher than the thermodynamic equilibrium hydrate formation pressure (P_eq) to ensure the formation of hydrate so that the accurate prediction of P_eq is the basis of the determination of HBGS pressure. In this work, the P_eq of the helium-rich natural gases with different helium contents (1 mol%, 10 mol%, and 50 mol%) in gas and different tetrahydrofuran (THF) contents (5 wt%, 10 wt%, and 19 wt%) in liquid at different temperatures were experimentally investigated through the isothermal pressure search method. A new thermodynamic model was proposed to predict the P_eq of helium-rich natural gas. This model can quantitatively describe the effects of THF and helium on P_eq, and it predicts the P_eq of the helium-rich natural gases in this work accurately. The average relative deviation of the model is less than 3%. This model can guide the determination of the operating condition of the HBGS of helium-rich natural gas.