Voronov Vitaly P, Gorodetskii Evgeny E, Safonov Sergey S
Oil and Gas Research Institute, 3 Gubkin street, Moscow 119991, Russia.
J Phys Chem B. 2007 Oct 4;111(39):11486-96. doi: 10.1021/jp0724368. Epub 2007 Sep 11.
Using the experimental method of precision adiabatic calorimetry, the thermodynamic (equilibrium) properties of methane hydrate in quartz sand with a grain size of 90-100 microm have been studied in the temperature range of 260-290 K and at pressures up to 10 MPa. The equilibrium curves for the water-methane hydrate-gas and ice-methane hydrate-gas transitions, hydration number, latent heat of hydrate decomposition along the equilibrium three-phase curves, and the specific heat capacity of the hydrate have been obtained. It has been experimentally shown that the equilibrium three-phase curves of the methane hydrate in porous media are shifted to the lower temperature and high pressure with respect to the equilibrium curves of the bulk hydrate. In these experiments, we have found that the specific heat capacity of the hydrate, within the accuracy of our measurements, coincides with the heat capacity of ice. The latent heat of the hydrate dissociation for the ice-hydrate-gas transition is equal to 143 +/- 10 J/g, whereas, for the transition from hydrate to water and gas, the latent heat is 415 +/- 15 J/g. The hydration number has been evaluated in the different hydrate conditions and has been found to be equal to n = 6.16 +/- 0.06. In addition, the influence of the water saturation of the porous media and its distribution over the porous space on the measured parameters has been experimentally studied.
采用精密绝热量热实验方法,研究了粒径为90 - 100微米石英砂中甲烷水合物在260 - 290 K温度范围和高达10 MPa压力下的热力学(平衡)性质。得到了水 - 甲烷水合物 - 气体和冰 - 甲烷水合物 - 气体转变的平衡曲线、水合数、沿平衡三相曲线的水合物分解潜热以及水合物的比热容。实验表明,多孔介质中甲烷水合物的平衡三相曲线相对于块状水合物的平衡曲线向低温和高压方向移动。在这些实验中,我们发现,在测量精度范围内,水合物的比热容与冰的热容一致。冰 - 水合物 - 气体转变的水合物解离潜热为143±10 J/g,而从水合物转变为水和气体时,潜热为415±15 J/g。已在不同水合物条件下评估了水合数,发现其等于n = 6.16±0.06。此外,还通过实验研究了多孔介质的水饱和度及其在多孔空间中的分布对测量参数的影响。