陆相页岩吸附CH4的热力学特征——以鄂尔多斯盆地延长气田上三叠统延长组页岩为例

Thermodynamic characteristics of CH4 adsorption by continental shale: A case study of the Upper Triassic Yanchang Shale in the Yanchang Gasfield, Ordos Basin

为了完善等量吸附热的计算方法、明确陆相页岩吸附CH4的热力学特征、揭示其吸附机理,选取鄂尔多斯盆地延长气田上三叠统延长组长7段页岩岩样,开展了页岩吸附CH4的等温吸附实验并获得了过剩吸附量曲线,通过对比分析过剩吸附量与绝对吸附量之间的差异,阐明了基于不同类型吸附量的页岩等量吸附热特征。研究结果表明:①同一温度、压力条件下绝对吸附量大于过剩吸附量,绝对吸附量与过剩吸附量的差值在低温高压条件下较高,该差值与平衡压力符合指数函数变化关系,若采用过剩吸附量评价页岩储层的吸附性能,会造成评价结果偏低;②延长组页岩吸附CH4的绝对等量吸附热、过剩等量吸附热分别与绝对吸附量、过剩吸附量呈线性正相关关系,吸附质分子间的作用力对等量吸附热的影响占主导;③绝对等量吸附热小于过剩等量吸附热,相对误差介于18.18%~49.79%,并且在低吸附量阶段相对误差较大,如果采用过剩吸附量作为基础数据计算初始等量吸附热,计算结果会偏高,从而造成对吸附剂与吸附质分子间的作用力的评价结果偏高。

In order to improve the calculation method of the isosteric adsorption heat,clarify thermodynamic characteristics of CH4 adsorption by continental shale and reveal the adsorption mechanism,this paper selected shale samples from the seventh Member of Yanchang Formation of Upper Triassic in the Yanchang Gasfield of the Ordos Basin as the research object.The isothermal adsorption experiment was carried out on the CH4 adsorption by continental shale and the excess adsorption curves were plotted.Then,the characteristics of the isosteric adsorption heat of the shale with different types of adsorption capacity were illustrated by analyzing and comparing the difference between excess and absolute adsorption capacity.And the following research results were obtained.First,under the same temperature and pressure,absolute adsorption capacity is higher than the excess values.The difference between them is higher under low temperature and high pressure and it is in the relationship of exponential function with the equilibrium pressure.If excess adsorption capacity is used to evaluate the adsorptive property of shale reservoirs,the evaluation result will be underestimated.Second,for CH4 adsorption by Yanchang Formation shale,the absolute and excess isosteric adsorption heat values have a linear positive correlation with absolute and excess adsorption capacity respectively,and the intermolecular force of adsorbate has a dominant effect on isosteric adsorption heat values.Third,absolute isosteric adsorption heat value is less than the excess heat.The relative error is in the range of 18.18-49.79%,and it is higher in the stage with low adsorption capacity.If excess adsorption capacity is taken as the basic data to calculate initial isosteric adsorption heat values,the calculation result will overvalued,and consequently the evaluation on the intermolecular force of adsorbent and adsorbate is overestimated.