Direct Measurement of the Four-Phase Equilibrium Coexistence Vapor–Aqueous Solution–Ice–Gas Hydrate in Water–Carbon Dioxide System

Abstract

Precise data on the non-variant equilibrium of the four phases (vapor–aqueous solution–ice–gas hydrate) in P–T coordinates are highly desired for developing accurate thermodynamic models and can be used as reference points (similar to the triple point of water). Using the two-component hydrate-forming system CO2–H2O, we have proposed and validated a new express procedure for determining the temperature and pressure of the lower quadruple point Q1. The essence of the method is the direct measurement of these parameters after the successive formation of the gas hydrate and ice phases in the initial two-phase gas–water solution system under intense agitation of the fluids. After relaxation, the system occurs in the same equilibrium state (T = 271.60 K, P = 1.044 MPa), regardless of the initial parameters and the order of crystallization of the CO2 hydrate and ice phases. Considering the combined standard uncertainties (±0.023 K, ±0.021 MPa), the determined P and T values agree with the results of other authors obtained by a more sophisticated indirect method. Validating the developed approach for systems with other hydrate-forming gases is of great interest.

Experimental Measurements and Empirical Relationships on Permeability Evolutions of Water/Hydrate-Containing Muddy Reservoirs

“…In sandy hydrate reservoirs, temperature agitation affecting the phase transition process of hydrates has been studied. Temperature agitation leads to an increase in the potential energy of the movement of water molecules in sandy hydrate reservoirs. , At the same time, temperature agitation can also lead to the thermal dissociation of hydrates, producing large amounts of gas . The presence of temperature agitation also affects the elastic modulus of hydrate reservoirs .…”