Integrated Thermodynamic and Kinetic Modeling of Methane Hydrate Formation: Experimental Validation and Predictive Analysis

Abstract


Gas hydrate formation presents significant flow assurance challenges in oil and gas operations, particularly in subsea pipelines where low temperatures (< 290 K) and high pressures (>5 MPa) create ideal conditions for crystallization. This study integrates experimental and modeling approaches to characterize methane hydrate phase equilibria, the primary component of natural gas hydrates. Controlled stepwise heating experiments (0.3–1 K/hr) in a high-pressure reactor (50–130 bar range) precisely determined dissociation conditions with temperature uncertainty of ±0.1 K and pressure accuracy of ±0.05 MPa. A novel thermodynamic framework combining the PC-SAFT equation of state for chain molecule interactions, the CPA equation for hydrogen bonding effects, and Van der Waals-Platteeuw hydrate theory demonstrated exceptional predictive capability across the 280–290 K and 5.5–13 MPa operating window. The model's robustness was validated against four independent experimental datasets, achieving average absolute deviations of 1.55% for pressure and 0.05 % for temperature with the CPA approach, outperforming PC-SAFT in high-pressure regimes.The study also investigated kinetic behavior using two experimental methods, with Method B (post-cooling gas injection) providing unambiguous induction time measurements. Results revealed critical insights into hydrate nucleation and dissociation dynamics, including the identification of equilibrium points at the intersection of heating-cooling curves. These findings advance fundamental understanding of hydrate thermodynamics while offering practical tools for pipeline design, operational optimization, and emergency response planning in Arctic and deepwater environments. The developed methodology bridges the gap between laboratory-scale data and field-scale applications, ensuring accurate hydrate stability predictions under industrial conditions.

Full Text

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About the authors

A. Afranejad

Perm National Research Polytechnic University

V. V Poplygin

Perm National Research Polytechnic University

I. S Poplygina

Perm National Research Polytechnic University

Xian Shi

China University of Petroleum

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