Abstract

Gas hydrates show great potential with regard to various technical applications, such as gas conditioning, separation and storage. Hence, there has been an increased interest in applied gas hydrate research worldwide in recent years. This paper describes the development of an energetically promising, highly attractive rapid gas hydrate production process that enables the instantaneous conditioning and storage of gases in the form of solid hydrates, as an alternative to costly established processes, such as, for example, cryogenic demethanization. In the first step of the investigations, three different reactor concepts for rapid hydrate formation were evaluated. It could be shown that coupled spraying with stirring provided the fastest hydrate formation and highest gas uptakes in the hydrate phase. In the second step, extensive experimental series were executed, using various different gas compositions on the example of synthetic natural gas mixtures containing methane, ethane and propane. Methane is eliminated from the gas phase and stored in gas hydrates. The experiments were conducted under moderate conditions (8 bar(g), 9–14 °C), using tetrahydrofuran as a thermodynamic promoter in a stoichiometric concentration of 5.56 mole%. High storage capacities, formation rates and separation efficiencies were achieved at moderate operation conditions supported by rough economic considerations, successfully showing the feasibility of this innovative concept. An adapted McCabe-Thiele diagram was created to approximately determine the necessary theoretical separation stage numbers for high purity gas separation requirements.

Highlights

  • In recent decades, the importance of gas hydrate research has expanded exponentially

  • The induction times clearly show that spraying resulted in immediate nucleation after the start of the injection recycle with one exception, spraying test number three

  • Small proportions of ethane and propane were found in the hydrate phase, with 3 mol% each. These results clearly show that a natural gas mixture can be separated by means of a rapid gas hydrate formation process

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Summary

Introduction

The importance of gas hydrate research has expanded exponentially. Ice-like inclusions of gases in various water structures. All of these structures consist of small dodecahedral cages and larger cages with attached hexagonal or square surfaces that vary in size and ratio [1]. Natural gas hydrates are found worldwide, especially in the form of oceanic reserves, offshore and submarine, along continental slopes, for example, off the coasts of the United States (Hydrate Ridge) and China (South China Sea), as well as in permafrost (e.g., Canada, Mackenzie Delta; Russia, Messoyakah Field) [1,2]. Earlier but still persistent and ongoing research concerning gas hydrates was in the field of flow assurance, especially in inhibition research [14,15,16,17,18,19,20,21,22], to prevent the plugging of pipelines and related equipment by unintended hydrate formation

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