气体吸附过程肥煤纳米孔隙原位变形规律及机理

In-situ deformation behavior and mechanisms of fat coal nanopores during the gas adsorption process

  • 摘要: 纳米孔隙是煤中气体的主要吸附位点,直接影响煤中气体吸附、解吸和扩散能力。本文利用自行研制的基于小角X射线散射技术(SAXS)的气体高压吸附解吸装置和同步辐射小角X射线散射实验站,探究不同气体种类(CH4、CO2、N2)及气体压力对吸附过程煤体纳米孔隙变化特征的影响。使用Materials Studio软件采用巨正则蒙特卡罗模拟方法,使用Sorption模块进行3种气体的吸附模拟,设置0.5、1.0、2.0、3.0、5.0 nm 5种狭缝孔隙尺寸的吸附体系,进一步探究纳米孔隙、吸附压力、吸附气体种类和相互作用能之间的内在联系,揭示气体吸附过程肥煤纳米孔隙原位变形机理。研究表明:在1.0 MPa的吸附压力作用下,煤体吸附CH4、CO2和N2 3种气体时,煤体孔隙率最大值依次为19.57%、20.24%、19.37%,煤体比表面积最大值依次为9.83、10.53、8.84 m2/g,吸附CO2气体时对煤体孔隙率及比表面积影响最大。探究煤体吸附CH4气体时,气体吸附压力与煤体的孔隙率和比表面积呈正相关。伴随煤纳米孔隙的增加,削弱了煤大分子与气体分子间的相互作用力,相互作用能呈现减小趋势;且在2 nm的同一纳米孔隙尺寸的吸附模拟体系中,CO2气体与煤大分子间的相互作用能明显大于CH4和N2,且3种气体分子的吸附势能由高到低依次为:CO2 > CH4 > N2,进一步揭示了相互作用能与纳米孔隙变形的内在关系。

     

    Abstract: Nanopores serve as the primary adsorption sites for gases in coal, directly influencing the gas adsorption, desorption, and diffusion capacities. This study employs a self-developed high-pressure gas adsorption-desorption apparatus based on small-angle X-ray scattering (SAXS) technology and a synchrotron radiation SAXS experimental station to investigate the effects of different gas types (CH4, CO2, N2) and gas pressures on the evolution characteristics of nanopores in coal during the adsorption process. Using the grand canonical Monte Carlo simulation method in Materials Studio software, the Sorption module was utilized to simulate the adsorption of three gases. Adsorption systems with five slit pore sizes (0.5 nm, 1.0 nm, 2.0 nm, 3.0 nm, and 5.0 nm) were established to further explore the intrinsic relationships among nanopores, adsorption pressure, gas types, and interaction energy, thereby revealing the in-situ deformation mechanism of nanopores in fat coal during gas adsorption. The results indicate that under an adsorption pressure of 1.0 MPa, the maximum porosity values of coal adsorbing CH4, CO2, and N2 are 19.57%, 20.24%, and 19.37%, respectively, while the maximum specific surface area values are 9.83 m2/g, 10.53 m2/g, and 8.84 m2/g, respectively. The adsorption of CO2 has the most significant impact on coal porosity and specific surface area. When investigating CH4 adsorption, a positive correlation is observed between gas adsorption pressure and both porosity and specific surface area of coal. As the number of nanopores increases, the interaction force between coal macromolecules and gas molecules weakens, leading to a decreasing trend in interaction energy. Moreover, in adsorption simulation systems with the same nanopore size of 2 nm, the interaction energy between CO2 and coal macromolecules is significantly greater than that of CH4 and N2. The adsorption potential energy of the three gas molecules follows the order: CO2 > CH4 > N2, further elucidating the intrinsic relationship between interaction energy and nanopore deformation.

     

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