کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
216364 | 1426269 | 2012 | 6 صفحه PDF | دانلود رایگان |

We suggest two types of new amine-type sII formers: pyrrolidine and piperidine. These guest compounds fail to form clathrate hydrate structures with host water, but instead have to combine with light gaseous guest molecules (methane) for enclathration. First, two binary clathrate hydrates of (pyrrolidine + methane) and (piperidine + methane) were synthesized at various amine concentrations. 13C NMR and Raman analysis were done to identify the clathrate hydrate structure and guest distribution over sII-S and sII-L cages. XRD was also used to find the exact structure and corresponding cell parameters. At a dilute pyrrolidine concentration of less than 5.56 mol%, the tuning phenomenon is observed such that methane molecules surprisingly occupy sII-L cages. At the critical guest concentration of about 0.1 mol%, the cage occupancy ratio reaches the maximum of approximately 0.5. At very dilute guest concentration below 0.1 mol%, the methane molecules fail to occupy large cages on account of their rarefied distribution in the network. Direct-release experiments were performed to determine the actual guest compositions in the clathrate hydrate phases. Finally, we measured the clathrate hydrate phase equilibria of (pyrrolidine + methane) and (piperidine + methane).
Pyrrolidine and piperidine act as sII clathrate hydrate formers under methane gas.Figure optionsDownload as PowerPoint slideHighlights
► New sII clathrate hydrate formers were proposed: pyrrolidine and piperidine.
► Formation of gas hydrate with methane as help gas was confirmed.
► NMR, Raman, and XRD patterns were analyzed to identify the hydrate structures.
► We measured (L + H + V) phase equilibrium with proposed hydrate formers.
► Tuning phenomena increase gas storage in (pyrrolidine + CH4) clathrate hydrates.
Journal: The Journal of Chemical Thermodynamics - Volume 44, Issue 1, January 2012, Pages 20–25