Usage of the Kolmogorov−Johnson−Mehl−Avrami Model for the Study of the Kinetics of the Formation of Natural Gas Hydrate in Inverse Oil Emulsions

Abstract

The article presents the results of a study of the hydration of the aqueous phase in inverse oil emulsions with natural gas rich in methane (more than 90 vol.%). The aim of the work was to study the kinetics of the crystallisation of oil emulsions during the formation of natural gas hydrates in them using the method of differential scanning calorimetry (DSC).
The objects of the study were inverse oil emulsions containing 20, 40, 60, and 80 wt% of water. DSC is used under quasiequilibrium experiment conditions to study the kinetics of hydration of oil emulsions with gas.
The study showed the applicability of the Kolmogorov−Johnson−Mehl−Avrami model (KJMA) in order to describe the crystallisation process of inverse oil emulsions in a quasi-equilibrium DSC experiment. The kinetic parameters of the KJMA model in emulsions were determined for the processes of water drops conversion into ice, as well as their hydration with natural gas. It was shown that within the system “natural gas-oil-water” the process of ice formation is characterised by high values of the Avrami exponent (n > 3) and the degree of freedom (l = 3), and the process of natural gas hydrate formation
is characterised by low values of the Avrami exponent (n < 3) and medium degree of freedom (l = 1-3). It was shown that in a continuous aqueous phase, natural gas hydrates are formed by instantaneous nucleation in the form of separate onedimensional crystals; while in oil, hydrates are nucleated at a constant rate and, depending on the water content, grow in the form of disparate crystallites, shell, or spherulites. The obtained research results make it possible to deepen our knowledge of the kinetics and hydration mechanisms in oil emulsions, they can be used to complement the scientific basis
for creating new technologies for the joint transportation of oil and hydrated natural gas in it.

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