Anomalous KHI-Induced dissociation of gas hydrates inside the hydrate stability zone: Experimental observations & potential mechanisms

In the past decade, the low dosage hydrate inhibitors (LDHIs) - which include kinetic hydrate inhibitors (KHIs) and anti-agglomerants (AAs) - have seen increasing use for gas hydrate prevention in hydrocarbon production operations, offering significant CAPEX/OPEX advantages over traditional thermodynamic inhibitors (e.g. methanol, glycols). Typically dosed at < 2.5% in produced water, KHIs were historically considered primarily as hydrate nucleation inhibitors, although in recent years focus has shifted towards their powerful crystal growth inhibition properties. Beginning at low aqueous concentrations, KHI polymers induce a number of highly repeatable, well-defined, hydrate crystal growth inhibition (CGI) regions as a function of subcooling, varying from complete inhibition, through long induction times and reduced growth rates, to final failure/uninhibited growth. This behaviour can be used to robustly assess KHIs for field use, as we have previously demonstrated through development of the KHI CGI evaluation method, which is now used as standard by a number of laboratories. During CGI testing, it is not uncommon to observe anomalous (should be stable thermodynamically) hydrate dissociation in the presence of KHIs, although very little is understood regarding this phenomenon. In this work, we present the initial findings of experimental studies aimed at investigating this anomalous dissociation for different commercial base polymers. Results demonstrate that, in addition to inhibiting hydrate growth/nucleation, low dosages (e.g. 0.5% and 0.25%) of KHI polymers can induce partial or complete hydrate dissociation, with this process largely generic to different KHIs. However, some KHI polymers cause catastrophic hydrate growth after nucleation begins and these polymers show no ability to dissociate hydrates, so this hydrate dissociation ability is not universal to all KHI Polymers. The cause of this dissociation is unclear, although it is postulated to result from interactions between the KHI and inherent hydrate morphological and/or structural changes. In addition to improving confidence in KHI field use, findings potentially have novel applications with respect to hydrate plug remediation and gas production from naturally occurring hydrates in oceanic/permafrost sediments.