화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of Industrial and Engineering Chemistry, Vol.78, 186-197, October, 2019
DOI10.1016/j.jiec.2019.06.015  Export Citation
New perspectives on supercritical methane adsorption in shales and associated thermodynamics
Xu Tang1, 2, †, Nino Ripepi3, Sean Rigby4, Robert Mokaya1, and Ellen Gilliland3
  • 1School of Chemistry, University of Nottingham, Nottingham NG7 2RD, UK
  • 2Key Laboratory of Petroleum Resources Research, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
  • 3Department of Mining and Minerals Engineering, Virginia Polytechnic Institute and State University, Blacksburg, VA 24060, United States, USA
  • 4Department of Chemical and Environmental Engineering, University of Nottingham, Nottingham NG7 2RD, UK
E-mail:
Understanding methane adsorption behavior in shales is fundamental for optimizing shale gas development as the adsorbed methane is a large portion of the subsurface shale gas resource. However, the adsorption mechanism of supercritical methane in shales and associated thermodynamics are poorly understood because the equation of state of the adsorbed methane is unmeasurable. This work analyzed adsorption equilibria (up to 32 MPa and 393.15 K) using a rigorous framework that can account for nonideal gas properties and accurately extrapolate absolute adsorption uptakes from measured adsorption isotherms. The framework also allowsy a straightforward calculation of thermodynamic potentials relevant to adsorption such as enthalpy and entropy. Modelling results show that methane adsorption isotherms in shale under different pressures and temperatures are represented by a two dimensional adsorption isotherm surface. The density of the adsorbed methane in shales depends on temperature and pressure, which is always lower than the liquid methane density but higher than the corresponding gaseous methane density. The temperature-dependent and pressure-dependent characteristics of adsorbed methane density leads to the corresponding temperature-dependent and pressure-dependent measured/absolute adsorption isotherms. The maximum adsorption uptake of shales is independent of temperature and pressure. The isosteric enthalpy/entropy of adsorption and enthalpy/entropy of adsorbed methane are found to be temperature- and surface coverage-dependent. These new findings therefore not only clarify some historical misunderstandings of methane adsorption in shales for engineering application, but also provide a novel framework for interpreting methane adsorption behavior in shales and for determining the associated thermodynamics.
Keywords:Shale;Methane;Adsorption;Enthalpy;Adsorbed density
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