Raman Spectroscopy Study on Ternary Model Coal Mine Methane Hydrates.

Abstract

The microfeatures of coal mine methane (CMM) hydrates, synthesized with three gas samples (CH4/C2H6/N2, G1 = 43 : 47 : 10, G2 = 60 : 30 : 10, and G3 = 74 : 16 : 10) in a self-made transparent high-pressure cell at 275.15 K and 5 MPa were investigated using Raman spectroscopy. As a discriminator, the vibrational band frequencies in the C–C regions of the recorded hydrate Raman spectra for C2H6 show that G1∼G3 hydrates are structure I. The three principal parameters used to study the microfeatures of the model CMM hydrates, including cavity occupancies, hydrate guest compositions, and hydration numbers, were calculated. The large cavity occupancies for C2H6 constantly decrease from 85.12 to 79.32%, while the small cavity occupancies for CH4 have a continuous increase from 73.75 to 96.42%. However, CH4 competes with C2H6 on entering the large cavities for their large cavity occupancies of 12.79–17.31%. The cavity occupancies of N2 are less than 1.2%. The hydrate composition calculations show that the molar fractions of C2H6 are the maximum. The hydration numbers range from 6.221 to 6.00. Based on the hydrate guest compositions and hydration numbers, the molecular formulas of the three CMM hydrates are presented.