CSIRO Petroleum Resources, 26 Dick Perry Avenue, Kensington, Perth, WA 6151, Australia.
J Phys Chem B. 2010 May 13;114(18):6084-8. doi: 10.1021/jp910941d.
The effects of LMGS (large molecule guest substance) amount on the thermodynamics of natural gas hydrates, as well as structural characteristics of mixed hydrates of LMGS and natural gas, have been studied. The addition of 1.7 wt % neohexane (NH) to water induced inhibition of natural gas hydrates, and this inhibition effect increased with increased addition of NH up to 7.8 wt %. However, the hydrate equilibrium condition changed slightly when the concentration of NH further increased from 7.8 to 14.5 wt %. Investigations on structural characteristics were carried out by analyzing (13)C NMR spectra of mixed hydrates formed from the mixture of natural gas and NH. They indicate that two hydrate structures of II and H coexist simultaneously, and the ratio of structure H to II decreased from 0.97 to 0.43 when the NH concentration decreased from 14.5 to 7.8 wt %. In addition, it was confirmed that ethane, propane, and iso-butane gas molecules do not participate in the formation of structure H and only enclathrated in large cages of structure II. These results indicate the existence of multiple hydrate structures, which must be considered in many industrial applications when mixed hydrates are formed from multicomponent gas mixtures and liquid hydrocarbons.
研究了大分子客体物质(LMGS)含量对天然气水合物热力学以及 LMGS 和天然气混合水合物结构特性的影响。向水中添加 1.7wt%的正庚烷(NH)会抑制天然气水合物的形成,并且随着 NH 添加量的增加,这种抑制作用会增强,最高可达 7.8wt%。然而,当 NH 浓度进一步从 7.8wt%增加到 14.5wt%时,水合物平衡条件仅略有变化。通过分析由天然气和 NH 混合物形成的混合水合物的 (13)C NMR 谱进行了结构特性的研究。结果表明,同时存在 II 型和 H 型两种水合物结构,当 NH 浓度从 14.5wt%降低到 7.8wt%时,H 型与 II 型的比例从 0.97 降低到 0.43。此外,还证实乙烷、丙烷和异丁烷气体分子不参与 H 型结构的形成,仅被包合在 II 型结构的大笼中。这些结果表明存在多种水合物结构,当多组分气体混合物和液体烃形成混合水合物时,这在许多工业应用中必须加以考虑。