Thermodynamic inhibition of 4-methylmorpholine while forming sH hydrate with methane

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4-methylmorpholine (4-mMPL), a nitrogen-containing heterocyclic compound, is an organic base which acts as a proton acceptor. In this study, we characterized structure H (sH) clathrate hydrates with 4-mMPL by measuring the hydrate-phase equilibria and a series of microscopic analyzes (powder X-ray diffraction, solid-state C-13 NMR and Raman spectroscopy). 4-mMPL was found to have lower dissociation temperature at a given pressure compared to that of pure CH4 hydrate, simultaneously with a co-guest in sH hydrates (hexagonal P6/mmm). Such a change of thermodynamic stability is attributed to an oxygen atom in the molecular structure of 4-mMPL, which prevents hydrogen-bonding among water molecules. The ratio of the molecular diameter to cage diameter is 0.87, implying that the guest molecules can fit into cavities without distortion. The thermodynamic and chemical characteristics of 4-mMPL can be extended to other guest species in order to explain molecular behaviors related to inherent mechanisms of hydrate stability and host-guest interactions.
Publisher
PERGAMON-ELSEVIER SCIENCE LTD
Issue Date
2015-12
Language
English
Article Type
Review
Keywords

STRUCTURE-H-HYDRATE; CLATHRATE HYDRATE; STRUCTURE-II; HYDROGEN; RAMAN; STABILITY; FORMERS; STORAGE; GUESTS

Citation

CHEMICAL ENGINEERING SCIENCE, v.138, pp.347 - 352

ISSN
0009-2509
DOI
10.1016/j.ces.2015.08.027
URI
http://hdl.handle.net/10203/205137
Appears in Collection
ME-Journal Papers(저널논문)CBE-Journal Papers(저널논문)
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