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Adsorption characteristics and thermodynamic property fields of methane and Sichuan Basin shales

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Abstract

Adsorption of methane on three Sichuan Basin shales at 318 K, 338 K, and 358 K has been investigated experimentally. The adsorption equilibrium isotherm data were fitted with Langmuir, DR and DA model. A thermodynamic model on heat of adsorption (Qst), considering the non-ideality of gas and the adsorbed phase specific volume, was developed for adsorption fields of methane and shales. The other thermodynamic properties, included specific heat capacity of adsorbed phase (cp,a), entropy (sa) and enthalpy (ha) of adsorbed phase, were also evaluated on basis of the developed heat of adsorption model. The calculated isosteric heat of adsorption shows a temperature independent feature at lower surface loading while a negative temperature dependence at higher surface loading. Specific heat capacity of adsorbed phase (cpa) values increases with temperature, pressure and adsorption amount. The change of cpa value with temperature are higher at lower pressure and adsorption amount. The entropy and enthalpy of adsorbed phase decreases with the increase of methane adsorption, and the entropy change is larger at lower temperature suggesting lower temperature is conducive to formed ordered arrangement of CH4 molecules.

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Abbreviations

q:

adsorption amount /mmol·g-1

q0 :

limiting adsorption amount /mmol·g-1

P:

the equilibrium pressure /MPa

Psat :

saturated vapor pressure /MPa

qe :

adsorbate surface loading /mg

n:

fitting factor

va :

the adsorbed phase specific volume /cm3·g-1

vb :

specific volume of adsorbate at the boiling point /cm3·g-1

α:

thermal expansion expression /K-1

E:

the characteristics energy /J·mol-1

qL :

Langmuir saturated adsorption amount /mmol·g-1

b0 :

Langmuir equilibrium constant /MPa-1

R:

the ideal gas constant /J·mol-1

T:

temperature /K-1

Pc :

critical pressure /MPa

Tc :

critical temperature /K

ΔHv :

enthalpy of vaporization at standard boiling point /cal·g-1·mol-1

va :

the adsorbed phase specific volume /cm3·g-1

vv :

the gas phase specific volume /cm3·g-1

Cp,a :

adsorbed phase specific heat capacity /kJ·kg-1K-1

Cp,g :

gaseous phase specific heat capacity /kJ·kg-1·K-1

ha :

adsorbed phase entropy /kJ·kg-1

sa :

adsorbed phase entropy /kJ·kg-1·K-1

a:

adsorbed phase

g:

gaseous phase

b:

boiling point

0:

maximum or reference

c:

critical

sat:

saturation

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Acknowledgements

This work was supported by Chongqing Science and Technology Commission Projects (No. cstc2017jcyj-yszx0012 and cstc2018jcyj-yszx0016), Natural Science Foundation of Hebei Province (E2020402072), the Project of the State Key Laboratory of Laser Interaction with Matter (SKLLIM1813) and The Handan Science and Technology Research and development projects (19422091008-31).

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Authors and Affiliations

  1. State Key Laboratory of Coal Mine Disaster Dynamics and Control, Chongqing University, Chongqing, 400044, China

    Shuo Duan & Min Gu

  2. School of Mining and Geomatics Engineering, Hebei University of Engineering, Handan, 056038, Hebei, China

    Shuo Duan

  3. State Key Laboratory of Laser Interaction With Matter, Northwest Institute of Nuclear Technology, Xi’an, 710024, China

    Mengmeng Tao & Ke Huang

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  1. Shuo Duan
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Derivation of thermodynamic properties and Comparison of results of different adsorption heat models(Figure S1) are available in Supplementary Information.

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Duan, S., Gu, M., Tao, M. et al. Adsorption characteristics and thermodynamic property fields of methane and Sichuan Basin shales. Adsorption 28, 41–54 (2022). https://doi.org/10.1007/s10450-021-00352-6

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