煤吸附气体表面扩散的阻塞系数与模型

A surface diffusion block coefficient and model about coal-adsorbed gas

  • 摘要: 80%~90%的煤层气(煤矿瓦斯)以吸附态赋存,吸附态气体的扩散以表面扩散为主,对煤层气运移起决定性的作用。采用动力学与热力学方法,基于CHEN和YANG的表面扩散气体分子随机跳跃机制和吸附气体扩散过渡态理论,将表面扩散动力学参数与等量吸附热联合,推导了表面扩散阻塞系数(κ)的理论计算方法,建立了煤吸附气体表面扩散系数模型,并应用该模型讨论了温度、压力、等量吸附热和阻塞系数对表面扩散系数的影响。获得以下结论:① 建立了采用等量吸附热计算阻塞系数的方法。煤吸附气体过程中,0 < κ < 1;吸附达到平衡,气体分子向前和向后弹跳的概率相等,κ=1;理想状态下的无限空间的表面扩散,不存在阻塞,κ=0。② 构建了煤吸附气体表面扩散系数模型并经过验证。煤吸附气体表面扩散系数仅为等量吸附热、覆盖度和温度的函数,所需参数只用常规等温吸附实验即可获得,适用于低压至高压的全过程,模型简洁实用;经验证,所建立的模型与实验数据拟合度R2=0.74380.9834,表明该模型是可靠的。③ 讨论了温度、压力、等量吸附热和阻塞系数对表面扩散的影响。温度与表面扩散系数呈线性正相关,压力与表面扩散系数呈Langmuir方程形式变化,等量吸附热与表面扩散系数呈指数相关性,阻塞系数与表面扩散系数呈幂函数相关性。④ 煤层气表面扩散在微观上是吸附气体分子的活化跳跃过程(由吸附势差引起的活化),在宏观上可视为由浓度梯度驱动。研究结果丰富了对煤层气表面扩散行为的认识,并提供了一种利用热力学参数评价煤层气表面扩散系数的方法。

     

    Abstract: 80%−90% of coalbed methane(CBM)/coal mine gas is stored in adsorbed state, and the diffusion of adsorbed gas is dominated by surface diffusion, which plays a decisive role in the transportation of CBM. The paper adopts kinetic and thermodynamic methods, based on CHEN and YANG’s surface diffusion gas molecules random hopping mechanism and the transition state theory on the diffusion of adsorbed gases, deduces the theoretical calculation method of the surface diffusion block coefficient(κ) by combining the surface diffusion kinetic parameter with the isosteric heat of adsorption, and establishes the surface diffusivity model of coal-adsorbed gas. The effects of temperature, pressure, isosteric heat of adsorption, and the block coefficient on the surface diffusivity are discussed using the model. Gain the following conclusion: ① A method for calculating the block coefficient using isosteric heat of adsorption was developed. Coal adsorption of gases process, 0 < κ < 1; adsorption equilibrium, where gas molecules bounce forward and backward with equal probability, κ=1; surface diffusion in an ideal state of infinite space with no blockage, κ=0. ② The surface diffusivity model of coal-adsorbed gas is established and validated. The surface diffusivity of coal-adsorbed gas is only a function of the isosteric heat of adsorption, coverage and temperature, and the parameters can be obtained by conventional adsorption isothermal experiments, which is applicable to the whole process from low pressure to high pressure, and the model is simple and practical. It is verified that the developed model fits the experimental data with R2 = 0.74380.9834, indicating that the model is reliable. ③ The effects of temperature, pressure, isosteric heat of adsorption, and block coefficient on surface diffusion are discussed. The temperature is linearly and positively correlated with the surface diffusion coefficient, the pressure varies with the surface diffusivity in the form of the Langmuir equation, the isosteric heat of adsorption is exponentially correlated with the surface diffusivity, and the block coefficient is correlated with the surface diffusivity in the form of a power function. ④ CBM surface diffusion is an activation jump process of adsorbed gas molecules (activation caused by adsorption potential difference) at a micro level and is driven by concentration gradient at a macro level. The results enrich the knowledge of the surface diffusion behavior of CBM and provide a method to evaluate the surface diffusivity of CBM using thermodynamic parameters.

     

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