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温度/压力对甲烷超临界吸附能量参数的影响机制

Effect of temperature and pressure on energy parameters ofmethane supercritical adsorption

  • 摘要: 煤层气在储层高温高压环境中主要以超临界吸附状态赋存,温度和压力是影响煤储层含气性的重要外部控制因素,温压条件改变意味着煤-甲烷吸附体系的原始平衡状态被打破,体系能量发生变化。基于无烟煤等温吸附试验数据,通过Gibbs方程对比了甲烷超临界与亚临界吸附的差异,从吸附热力学和吸附动力学角度,分析了温度和压力对甲烷超临界吸附过程中的能量参数的影响规律。结果表明:超临界条件下的煤-甲烷吸附体系绝对吸附量大于过剩吸附量,二者间的差异随平衡压力增大而增大,随温度升高而减小。对于特定的煤-甲烷吸附体系,吸附势与吸附空间在任意温压条件下呈现单一吸附特征曲线关系,且平衡压力增加引起吸附势减小,吸附空间增大,而温度升高引起吸附势增大,吸附空间减少。甲烷分子主要以菲克型扩散方式在煤岩中传质,由于分子平均自由程受温压控制,扩散系数随压力增大而减小,随温度升高而增大。气体分子吸附活化能本质为分子动能的体现,不受体系压力影响,但受体系温度影响,温度越高,吸附活化能越大。

     

    Abstract: Coalbed methane mainly exists in supercritical adsorption state in high pressure and temperature environment. Pressure and temperature are the most important external factors that control the gas content of coal reservoirs. The changes in pressure and temperature indicate the breaking of initial equilibrium state of coal and methane adsorption system and the changes of system energy. In this paper, the difference between supercritical adsorption and subcritical adsorption was analyzed through the Gibbs equation using data from isothermal adsorption experiments. The effect of temperature and pressure on energy parameters of methane supercritical adsorption was analyzed from the aspects of adsorption thermodynamics and adsorption kinetics. The results show that the absolute adsorption volume of the coal-methane adsorption system is larger than the excess adsorption volume under supercritical conditions. The difference between the absolute adsorption volume and excess adsorption volume increases with the increase of equilibrium pressure and decreases with the increase of temperature. For a certain coal methane adsorption system, the relationship between adsorption potential and adsorption space remains the same under any pressure and temperature conditions. The increase of equilibrium pressure causes a decrease of adsorption potential and an increase of adsorption space,while the increase of temperature results in an increase of adsorption potential and a decrease of adsorption space. The diffusion mode of methane molecules in coals is Fick diffusion. The diffusion coefficient decreases with the increase of pressure and temperature as the average free path of gas molecules is affected by pressure and temperature. The adsorption activation energy of gas molecules is essentially kinetic energy, which is not controlled by pressure but is affected by temperature. The higher system temperature is associated with larger adsorption activation energy.

     

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