Determination of Hydrate Thermodynamic Equilibrium Data Using μDSC with Resolution Enhancement Employing Glass Microspheres

Abstract

Accurate determination of hydrate equilibrium properties is crucial for developing offshore oil and gas strategies and enabling technological applications in gas storage and transportation. This study presents a multicycle calorimetric method using glass microspheres to enhance resolution for determining hydrate equilibrium properties in CH4 + H2O systems, both uninhibited and inhibited with 10% or 30% MEG. In MEG-inhibited systems, merged peak clusters required Gaussian deconvolution to extract properties. Glass microspheres enhance calorimetric determination by improving signal resolution via increased surface area and induced nucleation, reducing experimental time. For noninhibited systems, Tonset is 294.3 K (300 bar) and 286.0 K (100 bar) with a 0.02% deviation. For inhibited systems, Tpeak is 285.0 K (100 bar, 10% MEG) and 276.4 K (100 bar, 30% MEG), and a deviation of up to 0.1%. In strongly MEG-inhibited systems, microspheres enable effective separation of overlapping dissociation peaks, making Gaussian deconvolution essential for accurate identification of equilibrium states. While the methodology also shows potential for measuring dissociation enthalpies in uninhibited systems (64 ± 2 kJ·mol–1), values diverged from references in MEG-inhibited systems (30 ± 2 kJ·mol–1, 10% MEG and 10.3 ± 0.6 kJ·mol–1, 30% MEG), indicating the inhibitor's high concentration influences the dissociation process itself.