差压穿透法煤吸附气体表面扩散系数测定方法

A method for measuring surface diffusion coefficient of coal-adsorbed gas using a differential pressure permeation method

  • 摘要: 煤吸附气体表面扩散行为难以测量和定量表征,一直是煤层气(煤矿瓦斯)运移规律研究中存在的问题或难点。采用吸附动力学方法,基于Maxwell-Stefan扩散理论,利用每次吸附平衡时体相与吸附相化学势改变量的一致性,推导了覆盖度依赖性表面扩散通量方程并以Fick定律形式表达;结合质量守恒方程,建立了差压下煤中两相气体传输统一模型,提出了差压穿透法测定煤吸附气体表面扩散系数的原理与实验方法,并应用差压穿透法测得了表面扩散系数和两相气体传输贡献度。结果表明:覆盖度依赖性表面扩散通量方程的表面扩散系数与Maxwell-Stefan扩散理论的表面扩散系数符合HIO模型关系,是Maxwell-Stefan扩散理论的延展,能用Arrhenius 方程形式表示,理论推导结果正确,可用于表征煤吸附气体表面扩散行为。差压下煤中两相气体传输统一模型描述了差压下煤中吸附气体和游离气体传输的统一过程,该模型结合煤体多尺度孔隙结构串联物理模型构建,考虑了煤吸附气体表面覆盖度的影响,为差压穿透法原理的基础。基于模型构建差压−时间关系式,利用表面扩散的敏感参数(差压−时间曲线)反演表面扩散系数,提出了差压穿透法原理。基于原理,设计了差压穿透法实验,搭设了差压穿透法实验装置,测得了差压−时间曲线。差压−时间关系式与差压−时间曲线拟合度R2达0.977 6,验证了差压穿透法原理,可从总的气体传输过程(差压−时间曲线)中提取表面扩散系数。实验的表面扩散系数可用原理中煤吸附气体表面扩散系数表征公式描述,拟合度R2达0.997 9,拟合参数D0s∞α在理论分析的取值范围之内,实验测定结果正确,可适用于煤中单组分气体且覆盖度为0~1内的表面扩散系数测定。在温度303 K,吸附平衡压力0.1~3 MPa,改变相同差压dp/dx实验条件下,煤吸附气体(甲烷−九里山煤样)表面扩散贡献度为95.70%~29.08%,游离气体运移贡献度为4.30%~70.92%,随着压力的降低,煤中气体运移过程由游离气体运移主导逐渐过渡为吸附气体表面扩散主导。实验结果表明煤中不仅存在吸附气体表面扩散行为,且在低压条件下(˂1.5 MPa),煤层气(煤矿瓦斯)运移过程会由吸附气体表面扩散主导(贡献度超过50%),煤吸附气体表面扩散行为不可忽略。评价煤中吸附气体的传输能力,可靠地预测吸附气体对煤层气(煤矿瓦斯)抽采效率的长期影响,煤吸附气体表面扩散系数的实验测定必不可少。

     

    Abstract: The surface diffusion behavior of coal-adsorbed gas is difficult to measure and quantitatively characterize, which has always been a problem or difficulty in the study of the migration law of coalbed methane (coal mine gas). The paper adopts the adsorption kinetics method, based on the Maxwell-Stefan diffusion theory, utilizes the consistency of the chemical potential change between the bulk phase and the adsorbed phase at each adsorption equilibrium to deduce the surface diffusion flux equation dependent on coverage and expressed in the form of Fick’s law; Combined with the mass conservation equation, a unified model for two-phase gas transport in coal under differential pressure is established, the principle and the experimental method for measuring the surface diffusion coefficient of coal-adsorbed gas using a differential pressure penetration method are proposed, and the surface diffusion coefficient and the contribution of two-phase gas transport are measured by the differential pressure penetration method. The results show that: The surface diffusion coefficient of the surface diffusion flux equation dependent on coverage conforms to the HIO model relationship with that of the Maxwell-Stefan diffusion theory. It is an extension of the Maxwell-Stefan diffusion theory, can be expressed in the form of the Arrhenius equation, and can be used to characterize the surface diffusion behavior of coal-adsorbed gas. The theoretical derivation result is correct. The unified model of two-phase gas transport in coal under differential pressure describes the unified process of adsorbed gas and free gas transport in coal under differential pressure. This model is constructed in combination with the physical model of coal multiscale pore structure in series, taking into account the influence of surface coverage of coal-adsorbed gas, and serves as the basis for the principle of differential pressure penetration method. Based on the model, the differential pressure-time relationship equation is constructed, the surface diffusion coefficient is inverted by using the sensitive parameter of surface diffusion (differential pressure-time curve), and the principle of the differential pressure penetration method is proposed. Based on the principle, the experiment of differential pressure penetration method is designed, and the experimental device of differential pressure penetration method is set up, and the differential pressure-time curve is measured. The fitting degree R2 of the differential pressure-time relationship equation and the differential pressure-time curve reached 0.977 6, verifying the principle of the differential pressure penetration method and indicating that the surface diffusion coefficient can be extracted from the total gas transport process (differential pressure-time curve). The surface diffusion coefficient measured by differential pressure penetration method can be described by the characteristic equation of surface diffusion coefficient of coal-adsorbed gas in the principle. The fitting degree R2 reaches 0.997 9, and the fitting parameters D0s∞ and α are within the value range of theoretical analysis, which indicates that the experimental results are correct and can be applied to the surface diffusion coefficient determination of single component gas in coal with a coverage of 0 to 1. Under the experimental conditions of temperature 303 K, adsorption equilibrium pressure 0.1~3 MPa, changing the same differential pressure dp/dx, the contribution of the surface diffusion of coal-adsorbed gas (methane-Jiulishan coal sample) is 95.70%~29.08%, and the contribution of the migration of free gas is 4.30%~70.92%. As the pressure decreases, the gas migration process in coal gradually transitions from being dominated by the migration of free gas to being dominated by the surface diffusion of adsorbed gas. The experimental results show that there is not only the surface diffusion behavior of adsorbed gas in coal, but also the migration process of coalbed methane (coal mine gas) will be dominated by the surface diffusion of adsorbed gas (contribution is more than 50%) under the low pressure condition (˂1.5 MPa), and the surface diffusion behavior of coal-adsorbed gas can not be ignored. To evaluate the transport capacity of adsorbed gas in coal and reliably predict the long-term impact of adsorbed gas on the extraction efficiency of coalbed methane (coal mine gas), the experimental measurement of the surface diffusion coefficient of coal-adsorbed gas is essential.

     

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