Abstract

Clathrate hydrate is considered to be a potential medium for gas storage and transportation. Slow kinetics of hydrate formation is a hindrance to the commercialized process development of such applications. The kinetics of methane hydrate formation from the reaction of ice powder and methane gas doped with/without saturated ethanol vapor at constant pressure of 16.55 ± 0.20 MPa and constant temperature ranging from −15 to −1.0 °C were investigated. The methane hydrate formation can be dramatically accelerated by simply doping ethanol into methane gas with ultralow ethanol concentration (<94 ppm by mole fraction) in the gas phase. For ethanol-doped system 80.1% of ice powder were converted into methane hydrate after a reaction time of 4 h, while only 26.6% of ice powder was converted into methane hydrate after a reaction time of 24 h when pure methane gas was used. Furthermore, this trace amount of ethanol could also substantially suppress the self-preservation effect to enhance the dissociation rate of methane hydrate (operated at 1 atm and temperatures below the ice melting point). In other words, a trace amount of ethanol doped in methane gas can act as a kinetic promoter for both the methane hydrate formation and dissociation.

Highlights

  • Clathrate hydrates have been widely explored and investigated since 1930s due to the flow assurance and safety concerns in oil and gas pipelines[3]

  • After 24 h, the reaction tank was depressurized to atmospheric pressure and connected to flow meter to determine the amount of methane released from the dissociation of methane hydrate

  • The dissociation process would maintain at the same temperature as the reaction temperature for converting methane hydrate back into ice for 9 h and the temperature of reaction tank was raised up to 15 °C to dissociate all the ice and methane hydrate remaining inside the system

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Summary

Introduction

Clathrate hydrates have been widely explored and investigated since 1930s due to the flow assurance and safety concerns in oil and gas pipelines[3]. Alcohols have been verified as kinetic promoters of clathrate hydrate formation from aqueous solutions[18,19] or ice particles[20,21,22,23]. Abay and Svartaas[19] measured the induction time of methane hydrate with ultralow concentration (ranging from 1.5 to 20 ppm by weight) methanol aqueous solution and determined the rate of nucleation and induction time by fitting the parameter of the nucleation probability distribution function. Their results indicated that methanol can act www.nature.com/scientificreports/. Their results indicated that with small quantities of methanol the propane hydrate formation rate can be substantially enhanced

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