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An improved, high pressure, stirred automated lag time apparatus (HPS-ALTA) was used to determine gas hydrate nucleation and growth rates from induction time measurements at fixed subcooling. The improved HPS-ALTA uses multiple thermoelectric elements to allow rapid, radially symmetric heating and cooling, which together with the automatic detection of hydrate formation, makes feasible the measurement of statistically significant induction time distributions. Four induction time probability distributions, with between 83 and 312 points, were measured at subcoolings ranging from (6 to 9.7) K for water with a synthetic natural gas mixture at pressures around 12 MPa. The induction time data measured at each subcooling were exponentially distributed and were fit using a model derived from Classical Nucleation Theory based on the mononuclear nucleation mechanism. The nucleation rates obtained in this work were consistent within a factor of three or better with recent literature measurements made using a completely different apparatus. Hydrate growth rates measured at fixed subcooling using the improved HPS-ALTA were also found to be stochastic but consistent with previous measurements of the kinetic growth rate in a binary gas mixture. The results obtained here establish the need to improve theoretical models of hydrate formation to reconcile predicted nucleation rates with the much slower ones observed experimentally. [ABSTRACT FROM AUTHOR]

Gas hydrate formation is a stochastic phenomenon of considerable significance for any risk-based approach to flow assurance in the oil and gas industry. In principle, well-established results from nucleation theory offer the prospect of predictive models for hydrate formation probability in industrial production systems. In practice, however, heuristics are relied on when estimating formation risk for a given flowline subcooling or when quantifying kinetic hydrate inhibitor (KHI) performance. Here, we present statistically significant measurements of formation probability distributions for natural gas hydrate systems under shear, which are quantitatively compared with theoretical predictions. Distributions with over 100 points were generated using low-mass, Peltier-cooled pressure cells, cycled in temperature between 40 and -5 °C at up to 2 K·min-1 and analyzed with robust algorithms that automatically identify hydrate formation and initial growth rates from dynamic pressure data. The application of shear had a significant influence on the measured distributions: at 700 rpm mass-transfer limitations were minimal, as demonstrated by the kinetic growth rates observed. The formation probability distributions measured at this shear rate had mean subcoolings consistent with theoretical predictions and steel-hydrate-water contact angles of 14-26°. However, the experimental distributions were substantially wider than predicted, suggesting that phenomena acting on macroscopic length scales are responsible for much of the observed stochastic formation. Performance tests of a KHI provided new insights into how such chemicals can reduce the risk of hydrate blockage in flowlines. Our data demonstrate that the KHI not only reduces the probability of formation (by both shifting and sharpening the distribution) but also reduces hydrate growth rates by a factor of 2. [ABSTRACT FROM AUTHOR]

• Statistically robust data for KHI impact on hydrate induction time probabilities. • KHIs modify induction time probabilities distributions from exponential to Gamma. • Data reveal how KHIs both delay formation and reduce crystal growth rate. • Mechanisms by which KHIs affect formation at various subcoolings elucidated. The formation of gas hydrates is crucial to many technological applications including energy production, energy storage, desalination, and CO 2 capture. Kinetic hydrate inhibitor (KHI) chemicals have been used industrially for over 25 years to suppress hydrate formation in key industrial applications. However the mechanisms by which they operate, and specifically whether they delay nucleation or just retard growth, remain open questions. Here induction time probability distributions for methane hydrates were measured at several constant subcoolings as a function of KHI concentration. This allowed the hydrate nucleation and growth rates at each condition to be separately quantified through the observed induction times and initial gas consumption rates, respectively. Adding a KHI produces a Gamma-distribution of induction times, characterized by two parameters: nucleation rate and the average number of events associated with detection. This is qualitatively different to the exponential distributions of induction time probabilities observed in systems without any KHI. These data reveal how KHIs both increase the nucleation work required to form a critical nuclei and increase the effective number of sites where nucleation could occur. By showing unambiguously how KHIs delay hydrate nucleation at low subcoolings, this work opens systematic pathways for developing improved chemicals for either hydrate inhibition or promotion. The approach to inhibitor testing demonstrated here may also help natural gas producers assess the costs and benefits of competing designs for hydrate management. [ABSTRACT FROM AUTHOR]

• Hydrate nucleation & growth studied in a high pressure stirred automated lag time apparatus. • Impact of kinetic inhibitors on formation probability & growth distributions quantified. • Data allow differentiation between KHI functional mechanisms in classical nucleation theory. • Concentration dependence of nucleation and growth allow KHI benefit-cost assessment. Kinetic hydrate inhibitors (KHIs) are polymeric based chemicals that delay the nucleation and/or suppress the growth rate of gas hydrate crystals. While KHIs have been used successfully to mitigate hydrate blockage risk during oil and gas production, the mechanisms by which they function remain unclear. In this work, multiple high-pressure stirred automated lag time apparatus (HPS-ALTA) were used to investigate the impact of a KHI on the subcooling formation probability distributions of methane hydrates and the subsequent initial growth rates. Over 3000 hydrate formation events were measured around 12 MPa using seven independent HPS-ALTA cells with KHI concentrations of up to 3 wt% in water. The addition of KHI made hydrate formation much less stochastic: significant reductions occurred in both the width of the formation probability distribution for a given cell, and in the offsets between distributions measured with different cells. Average initial hydrate growth rates were reduced by approximately a factor of 5 as KHI concentration increased, even though the average driving force (subcooling) increased by a factor of up to 3. However, above a KHI concentration of 0.3 wt%, a diminishing return was observed in both the nucleation delay and growth rate suppression. A Classical Nucleation Theory (CNT) framework was applied to investigate whether polymer adsorption onto active nucleation sites could explain the observed delay in formation onset. However, the CNT kinetic parameter extracted from the measured formation probability data increased with concentration, which is opposite to the dependence predicted by the polymer-adsorption model of nucleation suppression by KHIs. [ABSTRACT FROM AUTHOR]